MX2014010058A

MX2014010058A - Polymerization of compositions comprising a farnesene.

Info

Publication number: MX2014010058A
Application number: MX2014010058A
Authority: MX
Inventors: Adam Safir; Joseph G Doolan
Original assignee: Amyris Inc
Priority date: 2012-02-22
Filing date: 2012-12-13
Publication date: 2014-09-22
Also published as: JP6100284B2; CN104203989B; EP2817342B1; AU2012370447A1; CA2864663C; HK1202884A1; WO2013126129A1; JP2015511266A; US20150025193A1; ZA201405513B; SG11201404518PA; CA2864663A1; EP2817342A1; AU2012370447B2; KR20140130183A; CN104203989A; MX362264B

Abstract

Provided herein are polyfarnesenes such as farnesene homopolymers derived from a farnesene and farnesene interpolymers derived from a farnesene and at least a vinyl monomer; and the processes of making and using the polyfarnesenes. The farnesene homopolymer can be prepared by polymerizing the farnesene in the presence of a catalyst. In some embodiments, the farnesene is prepared from a sugar by using a microorganism.

Description

POLYMERIZATION OF COMPOSITIONS COMPRISING ÜN FARNESENO PREVIOUS RELATED REQUESTS This application claims the benefit in accordance with 35 U.S.C. § 119 (e) of the United States Provisional Patent Application Number: 61 / 653,401, filed on May 30, 2012 and the United States Provisional Patent Application Number: 61 / 601,562, filed on February 22, 2012, which are incorporated herein by reference in their entirety.

FIELD OF THE INVENTION This invention provides emulsion polymerization compositions comprising a farnesene and optionally at least one vinyl monomer; at least one emulsifier; and at least one free radical initiator. Also provided herein are methods for copolymerizing a polymerizable mixture or composition comprising a farnesene and at least one vinyl monomer in the presence of at least one free radical initiator.

BACKGROUND OF THE INVENTION The compounds of terpenes or isoprenoids are a large and varied class of organic molecules that can be produced by a wide variety of plants, such as conifers and some insects, such as swallowtail butterflies. Some isoprenoid compounds can also be made from organic compounds such as the sugars of microorganisms, including bioengineering microorganisms. Because the terpenes or isoprenoids compounds can be obtained from various renewable resources, they are ideal monomers for making ecological and renewable polymers.

The terpene polymers that are derived from the terpene or isoprenoid compounds are useful polymeric materials. For example, polyisoprene, polypenene and polyilimonen have been used in various applications such as in the manufacture of paper layers, adhesives, rubber compounds and other industrial products. Most existing terpene polymers derive generally from terpenes of 5 and 10 carbon atoms, for example, isoprene, limonene, myrcene, 3-carene, ocimene and pinene. These terpene monomers can be polymerized or copolymerized with other comonomers to form the corresponding homopolymers or terpene copolymers. However, polymers or copolymers of terpene or isoprenoid compounds having at least 15 carbon atoms are less known or do not exist. Due to its long chains, isoprenoid compounds, such as farnesene, farnesol, nerolidol, valencene, humulene, germacrene and elemeno, can provide polymers or copolymers with unique physical, chemical and biological properties.

There is a need for more polymers that are ecological and renewable, for example, polymers derived from isoprenoid compounds that can be obtained from natural resources. In addition, there is also a need for new polymers that have unique physical, chemical and biological properties.

COMPENDIUM OF THE INVENTION The needs mentioned in the above are met by various aspects described herein. In one aspect, there is provided herein an emulsion polymerization composition comprising: a) a polymerizable mixture comprising a farnesene and at least one vinyl monomer; b) at least one emulsifier; c) at least one free radical initiator; and d) water.

In another aspect, a method for the emulsion polymerization of a farnesene with at least one vinyl monomer is provided, wherein the method comprises the copolymerization of farnesene with at least one vinyl monomer in an aqueous medium in the presence of at least one free radical initiator and at least one emulsifier.

In another aspect, there is provided herein method for preparing a polymer emulsion, comprising: (a) providing an aqueous emulsion comprising a polymerizable mixture comprising a farnesene and at least one vinyl monomer; at least one emulsifier; at least one initiator; and water; and (b) emulsion polymerization of at least a portion of the polymerizable mixture to form the polymer emulsion. In some embodiments, the method further comprises a step of drying the polymer emulsion to form an emulsion polymer.

In some embodiments, the farnesene described herein is -farnesene or β-farnesene or a combination thereof. In certain embodiments, farnesene is in an amount greater than 20% by weight, greater than 50% by weight, greater than 60% by weight or greater than 70% by weight, based on the total weight of the polymerizable mixture. In some embodiments, farnesene is in an amount of about 20% by weight to about 50% by weight, based on the total weight of the polymerizable mixture. In certain embodiments, farnesene is in an amount of about 30% by weight to about 40% by weight, based on the total weight of the polymerizable mixture.

In certain embodiments, at least one vinyl monomer is styrene, substituted styrene, a diene of C-40 carbon atoms, a vinyl halide, vinyl ether, vinyl acetate, vinylpyridine, vinylidene fluoride, acrylonitrile, acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester, acrylamide, methacrylamide or a combination thereof. In some embodiments, at least one vinyl monomer comprises methacrylic acid and a methacrylic ester. In certain embodiments, the methacrylic ester is methyl methacrylate. In some embodiments, the methacrylic acid is in an amount of from about 0.1 wt% to about 5 wt% or from about 10 wt% to about 40 wt%, based on the total weight of the polymerizable mixture . In certain embodiments, at least one vinyl monomer further comprises an acrylic ester. In additional embodiments, the acrylic ester is butyl acrylate. In some embodiments, at least one vinyl monomer comprises methacrylic acid and styrene.

In certain embodiments, the free radical initiator is a water soluble free radical initiator. In certain embodiments, the water-soluble free radical initiator is ammonium peroxomonosulfate, ammonium peroxodisulfate, potassium peroxomonosulfate, potassium peroxodisulfate, sodium peroxomonosulfate, sodium peroxodisulfate, hydrogen peroxide, a redox initiator or a combination thereof .

In another aspect, an emulsion of polymers is provided herein which is prepared by a method described herein.

H.H In another aspect, an emulsion polymer that is prepared by a method described herein is provided herein. In some embodiments, the emulsion polymer is in the form of a film. In certain embodiments, the emulsion polymer is in the form of a powder.

In another aspect, there is provided herein a method for copolymerizing a polymerizable mixture in the presence of at least one free radical initiator to form a farnesene interpolymer, wherein the polymerizable mixture comprises a farnesene and at least one vinyl monomer, and wherein at least one free radical initiator is hydrogen peroxide, a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxy ester, a peroxy ketone, an azo compound, an organic polyoxide, a photoinitiator, a persulfate or a combination thereof.

In certain embodiments, farnesene is in an amount greater than 20% by weight, based on the total weight of the polymerizable mixture. In some embodiments, farnesene is a-farnesene, ß-farnesene or a combination thereof. In certain embodiments, at least one vinyl monomer is styrene, substituted styrene, a C4-4o diene carbon atom, a vinyl halide, vinyl ether, vinyl acetate, vinylpyridine, vinylidene fluoride, acrylonitrile, acrylic acid, an ester acrylic, methacrylic acid, a methacrylic ester, acrylamide, methacrylamide or a combination thereof. In some embodiments, at least one vinyl monomer comprises a methacrylic ester. In certain embodiments, at least one vinyl monomer comprises styrene. In some embodiments, at least one vinyl monomer comprises butadiene. In certain embodiments, at least one vinyl monomer comprises styrene and butadiene.

In another aspect, an interpolymer of farnesene is provided herein which is prepared by a method described herein.

Additional aspects of the invention and the characteristics and properties of various embodiments of the invention become apparent with the following description.

DESCRIPTION OF THE DRAWINGS Figure 1 depicts the Tg results of Examples 1-5 and 7-11.

Figure 2 represents the results of Tg of Examples 13-16.

DETAILED DESCRIPTION OF THE INVENTION General Definitions "Polymer" refers to a polymeric compound prepared by means of polymerized monomers, either of the same type or different. The generic term "polymer" it embraces the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer".

"Interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. The generic term "interpolymer" includes the term "copolymer" (which generally refers to a polymer prepared from two different monomers) as well as the term "terpolymer" which generally refers to a polymer prepared from three different monomers). It also encompasses polymers made by polymerizing four or more types of monomers.

"Organyl" refers to any organic substituent group, regardless of the functional type, which has a free valence in a carbon atom, for example, CH3CH2-, CICH2-, CH3C (= 0) -, 4-pyridylmethyl.

"Hydrocarbyl" refers to any univalent group formed by removing the hydrogen atom from a hydrocarbon, such as alkyl (e.g., ethyl), cycloalkyl (e.g., cyclohexyl), and aryl (e.g., phenyl).

"Heterocyclyl" refers to any univalent group formed by the removal of a hydrogen atom from any atom in the ring of a heterocyclic compound.

"Alkyl" or "alkyl group" refers to a group univalent having a general formula C n H 2n + i derived from the removal of a hydrogen atom from a branched or unbranched saturated aliphatic hydrocarbon, where n is an integer or an integer between 1 and 20, or between 1 and 8. examples of the alkyne groups include, but are not limited to, alkyl groups of 1-8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, -methyl-l-butyl, 3-methyl-l-butyl, 2-methyl-3-butyl, 2,2-dimethyl-l-propyl, 2-methyl-l-pentyl, 3-methyl-l-pentyl, -methyl-l-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2, 2-dimethyl-l-butyl, 3, 3-dimethyl-l-butyl , 2-ethyl-l-butyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl and octyl. Longer alkyl groups include nonyl and decyl groups. An alkyl group can be substituted or unsubstituted with one or more appropriate substituents. In addition, the alkyl group can be branched or unbranched. In some embodiments, the alkyl group contains at least 2, 3, 4, 5, 6, 7 or 8 carbon atoms.

"Cycloalkyl" or "cycloalkyl group" refers to a univalent group derived from a cycloalkane by removing a hydrogen atom from a non-aromatic, monocyclic polycyclic ring comprising carbon and hydrogen atoms. Examples of alkyl groups include, but are not limited to, cycloalkyl groups of 3-7 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, and cyclic and saturated bicyclic terpenes and cycloalkenyl groups of 3-7 carbon atoms, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptyl, and cyclic and unsubstantial bicyclic terpenes. A cycloalkyl group can be substituted or unsubstituted by one or two appropriate substituents. In addition, the cycloalkyl group can be monocyclic or polycyclic. In some embodiments, the cycloalkyl group contains at least 5, 6, 7, 8, 9 or 10 carbon atoms.

"Aryl" or "aryl group" refers to an organic radical derived from a monocyclic or polycyclic aromatic hydrocarbon by removing a hydrogen atom. Non-limiting examples of the aryl group include phenyl, naphthyl, benzyl, or tolanyl, sexyphenylene, phenanthrenyl, anthracenyl, coronenyl, and tolanylphenyl group. An aryl group can be substituted or unsubstituted with one or more appropriate substituents. In addition, the aryl group can be monocyclic or polycyclic. In some embodiments, the aryl group contains at least 6, 1, 8, 9 or 10 carbon atoms.

The "acrylic ester" refers to a compound that has the formula where R 'is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, heterocyclyl or heterocyclyl replaced. In certain embodiments, R 'is alkyl, cycloalkyl, aryl, alkaryl, arylalkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, substituted alkaryl or substituted arylalkyl. In some embodiments, R 'is methyl, ethyl, propyl, butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, decyl, isodecyl, lauryl, stearyl, hydroxyalkyl (eg, 2-hydroxyethyl), aminoalkyl (e.g. 2-aminoethyl, 2- (dimethylamino) ethyl or 2- (diethylamino) ethyl). In additional embodiments, R 'is substituted. Some non-limiting examples of acrylic ester include methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, n-hexyl acrylate, ethylhexyl acrylate, n-heptyl acrylate, 2-methylheptyl acrylate, octyl acrylate, isooctyl acrylate, n-nonyl acrylate, iso-nonyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, tridecyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, glycidyl acrylate, acrylate acetoacetoxyethyl, acetoacetoxypropyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, isodecyl acrylate, caprolactone acrylate, benzyl acrylate, hydroxyalkyl acrylates (for example, 2-hydroxyethyl acrylate), aminoalkyl acrylates ( for example, 2-aminoethyl acrylate, 2- (dimethylamino) ethyl acrylate, and 2- (diethylamino) ethyl acrylate), alkoxyalkyl acrylates (e.g., acrylates, ethoxyethyl 2-acrylate), aroxyalkyl acrylates (e.g., 2-phenoxyethyl acrylate) and combinations thereof.

The "methacrylic ester" refers to a compound which has the formula wherein R 'is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, heterocyclyl or substituted heterocyclyl. In certain embodiments, R 'is alkyl, cycloalkyl, aryl, alkaryl, arylalkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, substituted alkaryl or substituted arylalkyl. In some embodiments, R 'is methyl, ethyl, propyl, butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, decyl, isodecyl, lauryl, stearyl, hydroxyalkyl (e.g., 2-hydroxyethyl), aminoalkyl (e.g. 2-aminoethyl, 2 (dimethylamino) ethyl or 2- (diethylamino) ethyl). In additional embodiments, R 'is substituted. Some non-limiting examples of methacrylic ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, ethylhexyl methacrylate, n-heptyl methacrylate, 2-methylheptyl methacrylate, octyl methacrylate, isooctyl methacrylate, n-nonyl methacrylate, iso-nonyl methacrylate, decyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, acetoacetoxyethyl methacrylate, acetoacetoxypropyl methacrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, caprolactone methacrylate, hydroxyalkyl methacrylates (e.g., 2-hydroxyethyl methacrylate), aminoalkyl methacrylates (e.g., 2-aminoethyl methacrylate, 2- (dimethylamino) ethyl methacrylate , and 2- (diethylamino) ethyl methacrylate), alkoxyalkyl methacrylate (e.g., 2-ethoxyethyl methacrylate), aroxyalkyl methacrylate (e.g., 2-phenoxyethyl methacrylate) and combinations thereof.

"Alkoxycarbonyl" refers to a univalent group having the general formula R'0-C (= 0) -, where R 'is alkyl or substituted alkyl. In some embodiments, R 'is methyl, ethyl, propyl, butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, decyl, isodecyl, lauryl, stearyl, hydroxyalkyl (e.g., 2-hydroxyethyl), aminoalkyl (e.g. 2-aminoethyl, 2- (dimethylamino) ethyl or 2- (diethylamino) ethyl). In certain embodiments, alkoxycarbonyl is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, isopentoxycarbonyl, neopentoxycarbonyl, hexoxycarbonyl, heptoxycarbonyl, octoxycarbonyl, decoxycarbonyl, isodekoxycarbonyl, lauroxycarbonyl or stearoxycarbonyl. In certain embodiments, the alkoxycarbonyl is a substituted alkoxycarbonyl, such as hydroxyalkoxycarbonyl (e.g., 2-hydroxyethoxycarbonyl) and aminoalkoxycarbonyl (e.g., 2-aminoethoxycarbonyl, 2- (dimethylamino) ethoxycarbonyl or 2- (diethylamino) -ethoxycarbonyl).

"Vinyl monomer" refers to a compound having the formula (XV): wherein each of R5, R6, R7 and R8 is independently H, an organyl group or a functional group. In some embodiments, each of R5, R6, R7 and R8 is as defined herein.

"Isoprenoid" and "isoprenoid compound" are used interchangeably herein to refer to a compound that is derived from an isopentenyldiphosphate.

"Substituted" is used to describe a compound or the chemical portion refers to at least one hydrogen atom of the compound or the chemical portion that is replaced with a second chemical portion. The second chemical portion can be any desired substituent that does not adversely affect the desired activity of the compound. The Examples of substituents are those which are found in the exemplary compounds and in the embodiments described herein, as well as halogens; I rent; heteroalkyl; alkenyl; alkynyl; aryl, heteroaryl, hydroxyl; alkoxy; aroxyl; alkoxyalkoxy; Not me; nitro; thiol; thioether; imina; cyano; amido; phosphonate; phosphine; carboxyl; thiocarbonyl; sulfonyl; sulfonamide; acyl; formyl; acyloxy; alkoxycarbonyl; glycidyl; xyranyl; acetoacetoxy; oxo; haloalkyl (for example, trifluoromethyl); carbocyclic cycloalkyl, which may be fused or unfused monocyclic or polycyclic (eg, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl) or a heterocycloalkyl, which may be monocyclic or polycyclic fused or non-fused (eg, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl) or thiacinyl); carbocyclic or heterocyclyl, monocyclic or fused or non-fused polycyclic aryl (for example, phenyl, naphthyl, pyrrolyl, indolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, quinolinyl, isoquinolinyl, acridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, benzimidazolyl, benzothiophenyl or benzofuranyl); amino (primary, secondary or tertiary); o-lower alkyl; o-aryl, aryl; arylalkyl lower; -C02CH3; -CONH2; -OCH2CONH2; -NH2; -S02NH2; -OCHF2; -CF3; -OCF3; -NH (alkyl); -N (alkyl) 2; -NH (aryl); -N (alkyl) (aryl); -N (aryl) 2; -CHO; -CO (alkyl); -CO (aryl); -C02 (alkyl); and -CO2 (aryl); and such fractions can be optionally substituted by a fused ring structure or bridge, for example, -OCH20-. These substituents may be optionally substituted with a substituent selected from such groups. All chemical groups described herein may be substituted, unless otherwise specified.

"Organolithium reagent" refers to an organometallic compound with a direct bond between a carbon and a lithium atom. Some of the non-limiting examples of organolithium reagents include vinyl lithium, aryllithium (for example, phenyllithium), and alkyl lithium (for example, n-butyl-lithium, sec-butyl-lithium, -butyl lithium, methyl-lithium, isopropyl-lithium or other alkyl lithium reagents having from 1 to 20 carbon atoms).

A composition that is "basically free" of a compound means that the composition contains less than about 20% by weight, less than about 10% by weight, less than about 5% by weight, less than about 3% by weight. weight, less than about 1% by weight, less than about 0.5% by weight, less than about 0.1% by weight, or less than about 0.01% by weight of the compound, based on the total volume of the composition.

A polymer that is "basically linear" means that the polymer contains less than about 20% by weight, less than about 10% by weight, less than about 5% by weight, less than about 3% by weight, less than about 1% by weight, less about 0.5% by weight, less than about 0.1% by weight, or less than about 0.01% by weight of the branched, star-shaped or other regular or irregular structures, based on the total volume of the composition.

A polymer that is "basically branched" means that the polymer contains less than about 20% by weight, less than about 10% by weight, less than about 5% by weight, less than about 3% by weight, less about 1% by weight, less than about 0.5% by weight, less than about 0.1% by weight, or less than about 0.01% by weight of linear, star-shaped or other regular or irregular structures, based on the total volume of the composition.

A polymer that is "basically star-shaped" means that the polymer contains less than about 20% by weight, less than about 10% by weight, less than about 5% by weight, less than about 3% by weight. weight, less than about 1% by weight, less than about 0.5% by weight, less than about 0.1% by weight, or less than about 0.01% by weight of branched, linear or other regular or irregular structures, based on the total volume of the composition.

In the following description, all the numbers described herein are approximate values, regardless of whether the word "around" or "approximate" is used together with them. They can vary by 1 percent, 2 percent, 5 percent, or sometimes by 10 to 20 percent. Whenever a numerical margin with a lower limit, RL, and an upper limit, Ru, is described, any number that falls within the range is specifically described. In particular, the following numbers within the margin are specifically described: R = RL + k * (RU-RL), where k is a variable that varies from 1 percent to 100 percent with an increase of 1 percent, that is, k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, ..., 50 percent, 51 percent, 52 percent, ..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. In addition, any numerical range defined by two R numbers as defined in the above is also described in a specific manner.

The compositions described herein generally comprise a polyfarnesene and optionally a thickener. In other embodiments, the compositions described herein do not comprise a thickener. In other embodiments, the compositions described herein comprise a thickener.

In some embodiments, polyfarnesene is a homopolymer of farnesene, a farnesine interpolymer or a combination thereof. In certain embodiments, polyfarnesene is a homopolymer of farnesene comprising units derived from at least one farnesene such as o-farnesene, β-farnesene or a combination thereof. In other embodiments, the polyfarnesene is an interpolymer of farnesene comprising units derived from at least one farnesene and units derived from at least one copolymerizable vinyl monomer. In some embodiments, the farnesin interpolymer is derived from styrene and at least one farnesene. In other embodiments, the farnesin interpolymer is derived from methyl methacrylate and at least one farnesene. In other modalities, the farnesin interpolymer is derived from maleic anhydride and at least one farnesene. In other embodiments, the farnesin interpolymer is derived from methacrylic acid, styrene and at least one farnesene. In further embodiments, the farnesene interpolymer is derived from methacrylic acid, methyl methacrylate and at least one farnesene. In further embodiments, the farnesin interpolymer is derived from methacrylic acid, methyl methacrylate, butyl acrylate and at least one farnesene. In still other embodiments, the farnesene interpolymer is a random, block or alternating interpolymer. In still others modalities, the farneseno interpolymer is an interpolymer of diblock, triblock or another of multiple blocks.

In some embodiments, the homopolymer of farnesene is prepared by polymerizing β-farnesene in the presence of an appropriate catalyst to polymerize de? Ns such as ethylene, styrene or isoprene. In other embodiments, the homopolymer of farnesene comprises one or more units having the formula (I), (II), (III), (IV), a stereoisomer thereof or a combination thereof: where R1 has the formula (XI): R has the formula (XII) where each of m, n, 1 and k is independently an integer from 1 to around 5,000, from 1 to around 10,000, from 1 to around 50, 000, from 1 to around 100,000, from 1 to around 200,000, from 1 to around 500,000, from 2 to around 10,000, from 2 to around 50,000, from 2 to around 100,000, from 2 to around 200,000, or from 2 to around 500,000. In some modalities, each of m, n, 1 and k is independently an integer from 1 to 100,000. In other modalities, each of m, n, 1 and k is independently an integer from 2 to 100,000.

In certain embodiments, the farnesine homopolymer comprises at least one unit having the formula (I) wherein m is greater than about 300, greater than about 500 or greater than about 1000. In other embodiments, the homopolymer of farnesene comprises at least one unit having the formula (II) wherein n is greater than about 300, greater than about 500 or greater than about 1000. In other embodiments, the farneseno homopolymer comprises at least one unit having the formula ( III) where 1 is greater than about 300, greater than about 500 or greater than about 1000. In still other embodiments, the farneseno homopolymer comprises at least one unit having the formula (IV) where k is greater than about of 300, greater than about 500 or greater than about 1000.

In some embodiments, the homopolymer of farnesene comprises at least one unit having the formula (I) and at least one unit having the formula (II), where the sum of m and n is greater than about 300, greater than about 500 or greater than about 1000. In other embodiments, the farnesin homopolymer comprises at least one unit having the formula (I) and at least one unit having the formula (III), where the sum of m and 1 is greater than about 300, greater than about 500 or greater than about 1000. In other embodiments, the farnesene homopolymer comprises at least one unit having the formula (II) and at least one unit having the formula (III), where the sum of n and 1 is greater than about 300, greater than about of 500 or greater than about 1000. In still other embodiments, the farnesin homopolymer comprises at least one unit having the formula (I) and at least one unit having the formula (II) and at least one unit having has the formula (III), where the sum of m, n and 1 is greater than about 300, greater than about 500 or greater than about 1000. In still other embodiments, the farnesene homopolymer comprises at least one unit having the formula (I) and at least one unit having the formula (II) and at least a unit having the formula (III) and at least one unit having the formula (IV), where the sum of m, n, 1 and k is greater than about 300, greater than about 500 or greater than about 1000. In still other modalities, one or more of the units that have a formula (I), (II), (III) or (IV) in the homopolymer of farnesene described herein may be in any order.

In certain embodiments, the farnesene homopolymer is prepared by polymerizing α-farnesene in the presence of any suitable catalyst to polymerize olefins. In other embodiments, the farnesene homopolymer comprises one or more units having the formula (V), (VI), (VII), (VIII), a stereoisomer thereof or a combination thereof: where R has the formula (XIII) R has the formula (XIV) where each of m, n, 1 and k is independently an integer from 1 to about 5,000, of 1 to around 10,000, from 1 to around 50,000, from 1 to around 100,000, from 1 to around 200,000, from 1 to around 500,000, from 2 to around 10,000, from 2 to around 50,000, from 2 to around 100,000, from 2 to around 200,000, or from 2 to around 500,000. In some modalities, each of m, n, 1 and k is independently an integer from 1 to 100,000. In other modalities, each of m, n, 1 and k is independently an integer from 2 to 100,000.

In certain embodiments, the homopolymer of farnesene comprises at least one unit having the formula (V) wherein m is greater than about 300, greater than about 500 or greater than about 1000. In other embodiments, the homopolymer of farnesene comprises at least one unit having the formula (VI) wherein n is greater than about 300, greater than about 500 or greater than about 1000. In other embodiments, the farneseno homopolymer comprises at least one unit having the formula ( VII) where 1 is greater than about 300, greater than about 500 or greater than about 1000. In still other embodiments, the farneseno homopolymer comprises at least one unit having the formula (VIII) where k is greater than about of 300, greater than about 500 or greater than about 1000.

In some modalities, the homopolymer of farneseno comprises at least one unit that has the formula (V) and at least one unit having the formula (VI), where the sum of m and n is greater than about 300, greater than about 500 or greater than about 1000. In other embodiments, the farnesin homopolymer comprises at least one unit having the formula (V) and at least one unit having the formula (VII), where the sum of m and 1 is greater than about 300, greater than about 500 or greater than about 1000. In other embodiments, the farnesene homopolymer comprises at least one unit having the formula (VI) and at least one unit having the formula (VII), where the sum of n and 1 is greater than about 300, greater than about 500 or greater than about 1000. In still other embodiments, the homopolymer of farneseno comprises at least one unit having the formula (V) and at least one unit having the formula (VI) and at least one unit having the formula (VII), where the sum of m, n and 1 is greater than about 300, greater than about 500 or greater than about 1000. In still other embodiments, the farnesene homopolymer comprises at least one unit having the formula (V) and at least one unit having the formula (VI) ) and at least one unit that has the formula (VII) and at least one unit having the formula (VIII), where the sum of m, n, 1 and k is greater than about 300, greater than about 500 or greater than about 1000. In still other embodiments, one or more of the units having a formula (V), (VI), (VII) or (VIII) in the homopolymer of farnesene described herein may be in any order.

In some embodiments, the homopolymer of farnesene is prepared by polymerizing -farnesene and β-farnesene in the presence of any suitable catalyst to polymerize olefins. In other embodiments, the homopolymer of farnesene comprises one or more units having a formula (I), (II), (III), (IV), (V), (VI), (VII) or (VIII) described in present, a stereoisomer thereof or a combination thereof. In still other modalities, one or more of the units that have a formula (I), (II), (III), (IV), (V), (VI), (VII) or (VIII) in the homopolymer of Farnesene described herein may be in any order.

In some embodiments, the homopolymer of farnesene comprises two or more units having two different formulas selected from formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII), a stereoisomer thereof or a combination thereof. In other embodiments, such homopolymer of farnesene can be represented by the following formula: AxBy where each of x and y is at least 1, and where each of A and B has a formula independently (I), (II), (III ), (IV), (V), (VI), (VII) u (VIII) and A and B are different. In other embodiments, each of x and y is independently greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, or greater. In some embodiments, the A's and B's are joined in a substantially linear manner, the opposite to a substantially branched or substantially star-shaped manner. In other modalities, A and B are distributed randomly along the homopolymer chain of farnesene. In other embodiments, A and B are in two "segments" to provide a homopolymer of farnesene having a segmented structure, for example, AA-A-BB B. In other embodiments, A and B are distributed in a manner alternative along the chain of the homopolymer of farnesene to provide a homopolymer of farnesene having an alternative structure, for example, AB, ABA, ABAB, ABABA or the like.

In some embodiments, the homopolymer of farnesene comprises three or more units having three different formulas selected from formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII), a stereoisomer thereof or a combination thereof. In other embodiments, such farnesine homopolymer can be represented by the following formula: AxByCz where each of x, y, and z is at least 1, and where each of A, B and C has a formula independent (I), (II), (III), (IV), (V), (VI), (VII) or (VIII) and A, B and C are different. In other embodiments, each of x, y, and z is independently greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, or older. In some embodiments, the A, B and C are joined in a substantially linear manner, the opposite to a substantially branched or substantially star-shaped manner. In other modalities, the A, B and C are distributed randomly along the farnesine homopolymer chain. In other embodiments, the A, B and C are in three "segments" to provide a homopolymer of farnesene having a segmented structure, for example, AA-A-BB-B-CC-C. In other embodiments, the A, B and C are alternatively distributed along the chain of the farnesene homopolymer, to provide a homopolymer of farnesene having an alternative structure, for example, A-B-C-A-B, A-B-C-A-B-C or the like.

In certain embodiments, polyfarnesene is an interpolymer of farnesene. In other embodiments, the farnesene interpolymer is prepared by polymerizing at least one farnesene and at least one vinyl monomer in the presence of any suitable catalyst to polymerize vinyl de? Ns and monomers. In other embodiments, the farnesin interpolymer described herein comprises (a) one or more units having at least one of the formulas (I), (II), (III) and (IV) described herein; and (b) one or more units having the formula (IX): where p is an integer from 1 to around 5,000, from around 10,000, from 1 to around 50,000, from around 100,000, from 1 to around 200,000, from 1 to around 500,000, from 2 to around 10,000, from 2 to around 50, 000, from 2 to around 100,000, from 2 to around 200, 000, or from 2 to around 500, 000; and each of R5, R6, R7 and R8 is independently H, an organyl group, or a functional group. In some embodiments, each of R5, R6, R7 and R8 described herein is not a monovalent hydrocarbon group containing 4-8 carbon atoms. In some embodiments, each of R5, R6, R7 and R8 described herein is not an alkyl group containing 4-8 carbon atoms.

In some embodiments, the farnesin interpolymer described herein comprises (a) one or more units having at least one of the formulas (V), (VI), (VII) and (VIII) described herein; and (b) one or more units having the formula (IX) described herein: In other embodiments, the farnesin interpolymer described herein comprises (a) one or more units having at least one of formulas (I), (II), (III), (IV), (V), (VI) ), (VII) and (VIII) described herein; and (b) one or more units having the formula (IX) described herein: In some embodiments, the farnesene interpolymer is prepared by polymerizing at least one farnesene and at least two vinyl monomers in the presence of any suitable catalyst to polymerize olefins and vinyl monomers described herein. In certain embodiments, the farnesin interpolymer described herein comprises (a) one or more units having at least one of formulas (I), (II), (III), (IV), (V), (VI) ), (VII) and (VIII) described herein; (B) one or more units having the formula (IX): wherein each of R5, R6, R7 and R8 is independently H, alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl, alkynyl, heterocyclyl (e.g., pyridyl), alkoxy, aryloxy, carboxy (i.e., -COOH), alkoxycarbonyl (for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, (IX) isopropoxycarbonyl, n-butoxycarbonyl), aminoalkoxycarbonyl (e.g., 2-aminoethoxycarbonyl), hydroxyalkoxycarbonyl (e.g., 2-hydroxyethoxycarbonyl), aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy (e.g., CH3-C (= 0) -0), nitrile or halo (e.g., F, Cl, Br el); and (c) one or more units having the formula (IX): wherein R5 is carboxy or alkoxycarbonyl; R7 is H or alkyl; and each of R6 and R8 is independently H, and wherein each p is independently an integer from 1 to about 5. 000, from 1 to around 10,000, from 1 to around 50,000, from 1 to around 100,000, from 1 to around 200,000, from 1 to around 500,000, from 2 to around 10,000, from 2 to around 50,000 , from 2 to around 100,000, from 2 to around 200,000, or from 2 to around 500,000.

In some embodiments, the farnesene interpolymer is prepared by polymerizing at least one farnesene and at least two vinyl monomers in the presence of any catalyst suitable for the polymerization of olefins and vinyl monomers. In certain embodiments, the farnesin interpolymer described herein comprises (a) one or more units having at least one of formulas (I), (II), (III), (IV), (V), (VI), (VII) and (VIII) described herein; (B) one or more units having the formula (IX): wherein each of R5, R6, R7 and R8 is independently H, alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl, alkynyl, heterocyclyl (e.g., pyridyl), alkoxy, aryloxy, carboxy (i.e., -COOH), alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl), aminoalkoxycarbonyl (e.g., 2-aminoethoxycarbonyl), hydroxyalkoxycarbonyl (e.g., 2-hydroxyethoxycarbonyl), aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy (e.g. CH3-C (= 0) -O), nitrile or halo (for example, F, Cl, Br and I); (C) one or more units having the formula (IX): wherein each of R5 and R6 is independently carboxy or R5 and R6 together form -C (= 0) 0C (= 0) -; R7 is H or alkyl; and R8 is H; and (d) one or more units having the formula (IX): wherein R5 is alkoxycarbonyl; R7 is H or alkyl; and each of R6 and R8 is independently H, and wherein each p is independently an integer from 1 to about 5. 000, from 1 to around 10,000, from 1 to around 50,000, from 1 to around 100,000, from 1 to around 200,000, from 1 to around 500,000, from 2 to around 10,000, from 2 to around 50,000 , from 2 to around 100,000, from 2 to around 200,000, or from 2 to around 500,000.

In some embodiments, the farnesin interpolymer described herein is a random interpolymer. In other modalities, the farnesene interpolymer described herein is a random interpolymer where the vinyl monomer units and the farnesene units are randomly distributed. In other embodiments, the farnesin interpolymer described herein is a random interpolymer where the vinyl monomer units and the farnesine units are randomly distributed and where two or more of the formulas (I), (II), ( III), (IV), (V), (VI), (VII), (VIII) and (XI) in the farnesene units are distributed randomly, alternatively or in blocks.

In some embodiments, the farnesin interpolymer described herein is an alternative interpolymer. In other embodiments, the farnesene interpolymer described herein is an alternative interpolymer where the vinyl monomer units and the farnesine units are distributed in a alternative. In other embodiments, the farnesin interpolymer described herein is an alternative interpolymer where the vinyl monomer units and the farnesine units are randomly distributed and where two or more of the formulas (I), (II), (III) ), (IV), (V), (VI), (VII), (VIII) and (XI) in the farnesene units are distributed randomly, alternatively or in blocks.

In certain embodiments, the farnesin interpolymer is a block interpolymer having one or more first blocks comprising one or more units having the formula (I), (II), (III), (IV) or a combination of the same and one or more second blocks comprising one or more units having a formula (IX). In other embodiments, the farnesin interpolymer is a block interpolymer having one or more first blocks comprising one or more units having the formula (V), (VI), (VII), (VIII) or a combination of the same and one or more second blocks comprising one or more units having the formula (IX). In still other modalities, there is a first block and two second blocks and where the first block is between the two second blocks. In still other embodiments, each of the second blocks comprises units that are derived from styrene. In some embodiments, the farnesin block interpolymer is a polystyrene-polyfarnesene diblock polyfarnesene, polystyrene-polyfarnesene-polystyrene triblock polyfarnesene or a combination thereof.

In some embodiments, the farnesin interpolymer can be represented by the following formula: PxQy where each of x and y is the minor of 1, and where P has the formula (IX) and Q has the formula (I), (II), ( III), (IV), (V), (VI), (VII) or (VIII). In other embodiments, each of x and y is independently greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, or greater . In some embodiments, the P and the Q are joined in a substantially linear manner, the opposite to a substantially branched or substantially star-shaped manner. In other embodiments, P and Q are randomly distributed along the farnesin interpolymer chain. In other embodiments, the P and Q are in two or more blocks or segments to provide a farnesin interpolymer having a block structure, for example, PP-P-QQ Q or PP-P-QQ Q-P PP. In other embodiments, P and Q are alternatively distributed along the chain of the farnesin interpolymer to provide a farnesin interpolymer having an alternative structure, for example, P-Q, P-Q-P, P-Q-P-Q, P-Q-P-Q-P or the like. In some embodiments, each Q has a formula AxBy or AxByCz as described herein.

In certain embodiments, the amount of the formula (I) in the polyfarnesene described herein is greater than about 85% by weight, greater than about 80% by weight, greater than about 70% by weight, greater than about 60% by weight, or greater than about 50% by weight, based on the total volume of polyfarnesene. In other embodiments, the amount of the formula (III) in the polyfarnesene described herein is at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 40% by weight, at least about 50% by weight, at least about 60% by weight, at least about 70% by weight , at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, or at least about 99% by weight, based on the total weight of polyfarnesene. In other embodiments, the amount of the formula (II) in the polyfarnesene described herein is from about 1% by weight to about 99% by weight, from about 5% by weight to about 99% by weight, from about 10% by weight to about 99% by weight, or from about 15% by weight to about 99% by weight, based on the total weight of polyfarnesene. In still other embodiments, the amount of the formula (IV) in the polyfarnesene described herein is greater than about 0.1% by weight, greater than about 0. 5% by weight, greater than about 1% by weight, greater than about 2% by weight, or greater than about 3% by weight, based on the total weight of polyfarnesene. In some embodiments, the polyfarnesene described herein is substantially free of formula (I), (II), (III) or (IV).

In certain embodiments, the amount of formula (V), (VI), (VII) or (VIII) in the polyfarnesene described herein is greater than about 1% by weight, greater than about 5% by weight, greater than about 10% by weight, greater than about 20% by weight, greater than about 30% by weight, greater than about 40% by weight, greater than about 50% by weight, greater than about 60% by weight % by weight, greater than about 70% by weight, greater than about 80% by weight, or greater than about 90% by weight, based on the total weight of polyfarnesene. In other embodiments, the amount of formula (V), (VI), (VII) or (VIII) in the polyfarnesene described herein is at least about 1% by weight, at least about 2% by weight, at least about 3% by weight, at least about 5% by weight, at least about 10% by weight, at least about 20% by weight, at least about 30% by weight, at least about 40% by weight % by weight, at least about 50% by weight, at least about 60% by weight, based on the total weight of polyfarnesene. In other embodiments, the amount of the formula (V), (VI), (VII) or (VIII) in the polyfarnesene described herein is from about 1% by weight to about 99% by weight, from about 5% by weight to about 99% by weight, from about 10% by weight to about 99% by weight, or from about 15% by weight to about 99% by weight, based on the total weight of polyfarnesene. In some embodiments, the polyfarnesene described herein is substantially free of the formula (V), (VI), (VII) or (VIII).

In other embodiments, the sum of m and n described herein is greater than about 250, greater than about 300, greater than about 500, greater than about 750, greater than about 1000, or greater than about 2000. In other embodiments, the sum of m and 1 described herein is greater than about 250, greater than about 300, greater than about 500, greater than about 750, greater than about 1000, or greater than about 2000. In other embodiments, the sum of m, n and 1 described herein is greater than about 250, greater than about 300, greater than about 500, greater than about 750, greater than about 1000, or greater than about around 2000. In other embodiments, the sum of m, n, 1 and k described herein is greater than about 250, greater than about 300, greater than about 500, greater than about 750, greater than about 1000, or greater than around 2000.

In certain embodiments, the number average molecular weight (Mn), the weight average molecular weight (Mw), or viscosity average molecular weight (z) of the polyfarnesene described herein is greater than about 1,000, greater than about 5,000 , greater than about 10,000, greater than about 50,000, greater than about 100,000, greater than 200,000, greater than 300,000, greater than about 500,000, greater than 750,000, greater than 1,000,000, greater than 1,500,000, or greater than 2,000,000. In some embodiments, the Mn, Mw or Mz of the polyfarnesene described herein is less than about 10,000,000, less than about 5,000,000, less than about 1,000,000, less than about 750,000, less than about 500,000, less than about of 100,000, less than about 50,000, less than about 10,000, or less than about 5,000.

In some embodiments, the polyfarnesene described herein has at least a glass transition temperature (Tg) less than 50 ° C, less than 40 ° C, less than 30 ° C, less than 20 ° C, less than 10 ° C, less than 0 ° C, less than -10 ° C, less than -20 ° C, less than -30 ° C, less than -40 ° C, less than -50 ° C, less than -55 ° C, less than -60 ° C, less than -65 ° C, less than -70 ° C or less than -75 ° C, measured in accordance with AST D7426-08 entitled "Standard Test Method for the Assignment of the DSC Procedure to Determine the Tg of a Polymer or an Elastomeric Compound, which is incorporated herein by reference In some embodiments, the polyfarnesene described herein has at least one glass transition temperature (Tg) greater than 50 ° C, greater than 40 ° C, higher than 30 ° C, greater than 20 ° C, greater than 10 ° C, greater than 0 ° C, greater than -10 ° C, greater than -20 ° C, greater than -30 ° C, greater than -40 ° C , or greater than -50 ° C. In certain embodiments, the polyfarnesene has at least one vitreous transition temperature (Tg) of about -20 ° C to about 40 ° C, of about -15 ° C to about 35 ° C, about -10 ° C to about 30 ° C, about -5 ° C to about 25 ° C, about 0 ° C to about 20 ° C, or about 5 ° C ° C to around 15 ° C, as measured in accordance with ASTM D7426-08.

In some modalities, the amount of the formula (I) is greater than about 80% by weight, based on the total weight of polyfarnesene. In other embodiments, the sum of m, n and 1 is greater than about 300. In other embodiments, at least a portion of the double bonds in one or more of the formulas (I), (II), (III), ( IV), (IX), (XI), (XII) and the stereoisomers thereof are hydrogenated.

In some embodiments, polyfarnesene is an interpolymer of farnesene. In other embodiments, the farnesin interpolymer described herein comprises one or more units derived from a farnesene in an amount of at least about 5 mole percent, at least about 10 mole percent, at least about 15 mole percent, at least about 20 mole percent, at least about 30 mole percent , at least about 40 mole percent, at least about 50 mole percent, at least about 60 mole percent, at least about 70 mole percent, at least about 80 mole percent , or at least about 90 mole percent of the total farnesene interpolymer. In yet other embodiments, the farnesin interpolymer described herein comprises one or more units derived from a vinyl monomer in an amount of at least about 5 mole percent, at least about 10 mole percent, at least about of 15 mole percent, at least about 20 mole percent, at least about 25 mole percent, at least about 30 mole percent, at least about 40 mole percent, at least about of 50 mole percent, at least about 60 mole percent, at least about 70 mole percent, at least about 80 mole percent, or at least about 90 mole percent of the interpolymer of total farnesene.

In certain embodiments, polyfarnesene comprises one or more polymer molecules, each of the molecules independently has the formula (X '): where n is an integer from 1 to around 500, from 1 to around 1,000, from 1 to around 5,000, from 1 to around 10,000, from 1 to around 50, 000, from 1 to around 100 , 000, from 1 to around 200, 000 or from 1 to around 500,000; m is an integer from 0 to around 500, from 0 to around 1,000, from 0 to around 5,000, from 0 to around 10,000, from 0 to around 50,000, from 0 to around 100,000, from 0 to around 200,000 or from 0 to around 50,0000; X is derived from a farnesene; and Y is derived from a vinyl monomer, with the proviso that when m is 0, n is at least 2. In some embodiments, m is an integer from 1 to about 500, from 1 to about 1,000 , from 1 to around 5000, from 1 to around 10, 000, from 1 to around 50,000, from 1 to around 100, 000, from 1 to around 200,000 or from 1 to around 500,000. In certain modalities, the sum of n and m is from 2 to around 500, from 2 to around 1,000, from 2 to around 5,000, from 2 to around 10,000, from 2 to around 50, 000, from 2 to around from 100,000, from 2 to around 200,000 or from 2 to around 500,000.

In certain modalities, X has one or more of the where R1, R2, R3, R4 are as defined herein.

In certain modalities, Y has the formula (IX '): wherein each of R5, R6, R7 and R8 is independently H, an organyl group or a functional group. In some embodiments, each of R5, R6, R7 and R8 is independently H, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, heterocyclyl, substituted heterocyclyl or a functional group containing O, N, S, P or a combination of same.

In some embodiments, each of R5, R6, R7 and R8 is independently H, alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl, alkynyl, heterocyclyl (eg, pyridyl), alkoxy, aryloxy, carboxy (i.e., -COOH) , alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl), aminoalkoxycarbonyl (eg 2-aminoetoxicarbonilo), hidroxialcoxicarbonilo (for example, 2-hydroxyethoxycarbonyl), aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy (for example, CH3-C (= 0 ) -0), nitrile or halo (for example, F, Cl, Br and I).

In certain embodiments, the R 5 of the formula (X ') is carboxy; and R7 is H or alkyl. In other embodiments, R5 is alkoxycarbonyl; and R7 is H or alkyl. In some embodiments, the alkoxycarbonyl is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, isopentoxycarbonyl, neopentoxycarbonyl, hexoxycarbonyl, heptoxicarbonilo, octoxicarbonilo, decoxicarbonilo, isodecoxicarbonilo, lauroxicarbonilo or estearoxicarbonilo.

In some embodiments, R5 is hydroxyalkoxycarbonyl or aminoalkoxycarbonyl; and R7 is H or alkyl. In certain embodiments, the hydroxyalkoxycarbonyl is 2-hydroxyethoxycarbonyl; and the aminoalkoxycarbonyl is 2-aminoethoxycarbonyl, 2- (dimethylamino) ethoxycarbonyl or 2- (diethylamino) ethoxycarbonyl.

In certain embodiments, R 5 is 2-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2,4-dimethylphenyl or 4-fluorophenyl; and R7 is H. In certain embodiments, R5 is pyridyl or cyano; and R7 is H. In certain embodiments, R5 is acyloxy; and R7 is H. In certain embodiments, acyloxy is CH3C (= 0) -0-. In certain embodiments, R5 is halo; and R7 is H or halo. In some embodiments, R5 is chlorine; and R7 is H. In certain embodiments, R5 is fluoro; and R7 is fluorine.

In certain embodiments, the polyfarnesene comprises one or more polymer molecules, each of the molecules independently having the formula (X "): where n is an integer from 1 to around 500, from 1 to around 1,000, from 1 to around 5,000, from 1 to around 10, 000, from 1 to around 50, 000, from 1 to around from 100, 000, from 1 to around 200, 000 or from 1 to around 500,000; each of myk is independently an integer from 0 to around 500, from 0 to around 1,000, from 0 to around 5,000, from 0 to around 10,000, from 0 to around 50,000, from 0 to around 100,000 , from 0 to around 200, 000 or from 0 to around 500,000; X is derived from a farnesene; and each of Y and z is independently derived from a vinyl monomer, with the proviso that when m is 0 and k is 0, n is at least 2 In some embodiments, each of m and k is independently 1 to about from 500, from 1 to around 1,000, from 1 to around 5,000, from 1 to around 10,000, from 1 to around 50,000, from 1 to around 100,000, from 1 to around 200,000 or from 1 to around 500,000. In certain modalities, the sum of n, myk is independently from 3 to around 500, from 3 to around 1,000, from 3 to around 5, 000, from 3 to around 10,000, from 3 to around 50,000, from 3 to around 100, 000, from 3 to around 200, 000 or from 3 to around 500, 000.

In some modalities, the sum of n, m and k is greater than about 2, about 3, about 4, around 5, around 6, around 7, around 8, around 9 or around 10. In other modalities, the sum of n, myk is greater than around 15, around 20, around 25, around 30, around 35, around 40, around 45, around 50, around 55, around 60, around 65, around 70, around 75, around 80, around 85, around 90, around 95 or about 100 In additional modalities, the sum of n, myk is greater than about 500, about 1,000, about 1,500, about 2,000, about 3,000, about 4,000, about 5,000, about 6,000, about 7,000, about 8,000, about 9,000, about 10,000, about 50,000, about 100,000, about 500,000 or about 1,000,000.

In certain modalities, the sum of m and k is greater than about 2, about 3, about 4, around of 5, about 6, about 7, about 8, about 9 or about 10. In other modes, the sum of myk is greater than about 15, about 20, about 25, about 30, around 35, around 40, around 45, around 50, around 55, around 60, around 65, around 70, around 75, around 80, around 85, around 90, around 95 or around 100 In additional modalities, the sum of myk is greater than about 500, about 1,000, about 1,500, about 2,000, about 3,000, about 4,000, about 5,000, about 6,000, about 7,000, around 8,000, around 9,000, around 10,000, around 50,000 or around 100,000. In some modalities, the sum of myk is less than about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. In other modalities , the sum of myk is less than about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, around 70, around 75, around 80, around 85, around 90, around 95 or about 100 In additional modalities, the sum of myk is less than about 500, about 1,000, around 1,500, about 2,000, around 3,000, around 4,000, around 5,000, around 6,000, around 7,000, around 8,000, around 9,000, around 10,000, around 50,000 or around 100,000.

In some embodiments, each of myk is independently greater than 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. In other embodiments, each of myk is independently greater than about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, around 65, around 70, around 75, around 80, around 85, around 90, around 95 or around 100 In other modalities, each of myk is independently greater than about 500, around from 1,000, around 1,500, around 2,000, around 3,000, around 4,000, around 5,000, around 6,000, around 7,000, around 8,000, around 9,000, around 10,000. In certain modalities, each of myk is independently smaller than about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. In others modalities, each of myk is independently smaller than about 15, around 20, around 25, around 30, around 35, around 40, around 45, around 50, around 55, around 60, around 65, around 70, around 75, around 80, around 85, about 90, about 95 or about 100 In other modalities, each of myk is independently smaller than about 500, about 1,000, about 1,500, about 2,000, about 3,000, about 4,000 , around 5,000, around 6,000, around 7,000, around 8,000, around 9,000, around 10,000.

In some embodiments, X is as defined herein. In certain embodiments, each of Y, and z independently has the formula (IX '): where each of R5, R6, R7 and R8 is as defined herein.

In certain embodiments, R 5 of Y of the formula (X ") is carboxy or alkoxycarbonyl, R 7 of Y is H or alkyl, and each of R 6 and R 8 of Y is independently H. In some embodiments, R 5 of Z of the formula (X ") is alkoxycarbonyl, or hydroxyalkoxycarbonyl or aminoalkoxycarbonyl; R7 of Z is H or alkyl; and each of R6 and R8 of Z is independently H. In other embodiments, alkoxycarbonyl is the alkoxycarbonyl, is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, isopentoxycarbonyl, neopentoxycarbonyl, hexoxycarbonyl, heptoxycarbonyl, octoxycarbonyl, decoxycarbonyl, isodecoxycarbonyl, lauroxycarbonyl or stearoxycarbonyl; the hydroxyalkoxycarbonyl is hydroxyethoxycarbonyl; and the aminoalkoxycarbonyl is 2-aminoethoxycarbonyl, 2- (dimethylamino) ethoxycarbonyl or 2- (diethylamino) ethoxycarbonyl.

In some embodiments, R5 of Z of the formula (X ") is alkyl or aryl, and each of R6, R7 and R8 of Z is independently H. In certain embodiments, R5 of Z is aryl selected from phenyl, 2-methylphenyl , 4-methylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2,4-dimethyl-phenyl and 4-fluorophenyl.

In certain embodiments, R 5 of Y of the formula (X ") is alkoxycarbonyl or hydroxyalkoxycarbonyl, R 7 of Y is alkyl, and each of R 6 and R 8 of Y is H; R 5 of Z is alkoxycarbonyl; R 7 of Z is H or alkyl and each of R6 and R8 of Z is H. In some embodiments, R5 of Y of the formula (X ") is phenyl; each of R6, R7 and R8 of Y is H; R5 of Z is cyano; and each of R6, R7 and R8 of Z is H.

In some embodiments, the polyfarnesene comprises one or more polymer molecules, each of the molecules having independently formula (x '"): where n is an integer from 1 to around 500, from 1 to around 1, 000, from 1 to around 5,000, from 1 to around 10, 000, from 1 to around 50, 000, from 1 to around 100,000, from 1 to around 200, 000 or from 1 to around 500,000; each of m, k and 1 is independently an integer from 0 to about 500, from 0 to about 1,000, from 0 to about 5,000, from 0 to about 10, 000, from 0 to about 50, 000 , from 0 to around 100,000, from 0 to around 200, 000 or from 0 to around 500,000; X is derived from a farnesene; and each of Y, Z and Q is independently derived from a vinyl monomer, with the proviso that when m is 0, k is 0 and L is 0, n is at least 2 In some embodiments, each of m, k and 1 is independently from 1 to around 500, from 1 to around 1,000, from 1 to around 5, 000, from 1 to around 10,000, from 1 to around 50, 000, from 1 to around 100,000, from 1 to around 200,000 or from 1 to around 500,000. In certain modalities, the sum of n, m, k and 1 is independently from 4 to around 500, from 4 to around 1000, from 4 to around 5000, from 4 to around 10, 000, from 4 to around 50,000, from 4 to around 100, 000, from 4 to around 200,000 or from 4 to around 500,000.

In some modalities, the sum of n, m, k and 1 is greater than about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. In other embodiments, the sum of n, m, ky 1 is greater than about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, about 95 or about 100 In additional modalities, the sum of n, m, k and 1 is greater than about 500, about 1,000, around from 1,500, around 2,000, around 3,000, around 4,000, around 5,000, around 6,000, around 7,000, around 8,000, around 9,000, around 10,000, around 50,000, around 100,000, around 500,000 or around 1,000,000.

In certain modalities, the sum of m, k, and 1 is greater than about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. In other modalities, the sum of m, k and 1 is greater than about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, around 60, around 65, around 70, around 75, around 80, around 85, around of 90, about 95 or about 100 In additional modalities, the sum of m, k and 1 is greater than about 500, about 1,000, about 1,500, about 2,000, about 3,000, about 4,000, about 5,000, around 6,000, around 7,000, around 8,000, around 9,000, around 10,000, around 50,000 or around 100,000. In some modalities, the sum of m, k, and 1 is less than about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. In other modalities, the sum of m, k and 1 is less than about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, around 60, around 65, around 70, around 75, around 80, around 85, around 90, around 95 or around 100 In additional modalities, the sum of m, k and 1 is less than around of 500, about 1,000, about 1,500, about 2,000, about 3,000, about 4,000, about 5,000, about 6,000, about 7,000, about 8,000, about 9,000, about 10,000, about 50,000 or around 100,000.

In some modalities, each of m, k and 1 is independently greater than 1, about 2, about 3, about 4, about 5, about 6, about of 7, about 8, about 9 or about 10. In other modalities, each of m, k and 1 is independently greater than about 15, about 20, about 25, about 30, about 35, around 40, around 45, around 50, around 55, around 60, around 65, around 70, around 75, around 80, around 85, around 90, around 95 or around In other embodiments, each of m, k, and 1 is independently greater than about 500, about 1,000, about 1,500, about 2,000, about 3,000, about 4,000, about 5,000, about 6,000, about 7,000, around 8,000, around 9,000, around 10,000. In certain embodiments, each of m, k, and 1 is independently smaller than about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. In other modalities, each of m, K and L is independently smaller than about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about of 55, around 60, around 65, around 70, around 75, around 80, around 85, around 90, around 95 or around 100 In other modalities, each of m, k and 1 is independently less than about 500, about 1,000, about 1,500, around 2,000, about 3,000, about 4,000, about 5,000, about 6,000, about 7,000, about 8,000, about 9,000, about 10,000.

In some embodiments, X is as defined herein. In certain embodiments, each of Y, Z and Q independently has the formula (IX '): where each of R5, R6, R7 and R8 is as defined herein.

In some embodiments, R5 of Y of the formula (x '") is carboxy or alkoxycarbonyl, R7 of Y is H or alkyl, and each of R6 and R8 of Y is independently H. In some embodiments, R5 of Z of the formula (? "') is alkoxycarbonyl, hydroxyalkoxycarbonyl or aminoalkoxycarbonyl; R7 of Z is H or alkyl; and each of R6 and R8 of Z is independently H. In other embodiments, the alkoxycarbonyl is alkoxycarbonyl, is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, isopentoxycarbonyl, neopentoxycarbonyl, hexoxycarbonyl, heptoxycarbonyl, octoxycarbonyl, decoxycarbonyl, isodekoxycarbonyl, lauroxycarbonyl or stearoxycarbonyl; the hydroxyalkoxycarbonyl is hydroxyethoxycarbonyl; and the aminoalkoxycarbonyl is 2-aminoethoxycarbonyl, 2- (dimethylamino) ethoxycarbonyl or 2- (diethylamino) ethoxycarbonyl.

In some embodiments, each of R5 and R6 of Q of the formula (? "') Is carboxy or R5 and R6 together form -C (= 0) OC (= 0) -. In certain embodiments, R5 of Y of the formula (? "') is carboxy; R7 of Y is H or alkyl; and each of R6 and R8 of Y is independently H. In some embodiments, R5 of Z of the formula (? "') is alkoxycarbonyl, R7 of Z is H or alkyl, and each of R6 and R8 of Z is independently H. In some embodiments, R 5 of Q of the formula (x '") is alkyl or aryl; and each of R6, R7 and R8 of Q is independently H. In some embodiments, R5 of Q of the formula (? "') is alkoxycarbonyl, and each of R6, R7 and R8 of Q is independently H.

In general, polyfarnesene comprises a mixture in polymer molecules, each of which has the formula (X ') where each of n and m independently has a specific value. The average and distribution of the nominal values described herein depend on several factors such as the molar ratio of the initial materials, the reaction time and temperature, the presence or absence of a chain terminator, the amount of an initiator if any and the polymerization conditions. The farnesin interpolymer of the Formula (Xr) may include unreacted comonomers, although comonomer concentrations may be generally low, extremely low or undetectable. The extent of the polymerization, as specified by the n and m values, may affect the properties of the resulting polymer. In some modalities, n is an integer from 1 to around 5,000, from 1 to around 10,000, from 1 to around 50,000, from 1 to around 100, 000, from 1 to around 200,000, or from 1 to around 500,000; m is an integer from 0 to around 5,000, from 0 to around 10,000, from 0 to around 50,000, from 0 to around 100,000, from 0 to around 200,000, or from 0 to around 500,000. In other embodiments, n is independently from about 1 to about 5000, from about 1 to about 2500, from about 1 to about 1000, from about 1 to about 500, from about 1 to about 100 or from around 1 to around 50; and m is from about 0 to about 5000, from about 0 to about 2500, from about 0 to about 1000, from about 0 to about 500, from about 0 to about 100 or about 0 to about 50. A person skilled in the art will recognize that the additional average ranges of the n and m values are complete and are within the present description.

In some modalities ') or (X' '') comprises two groups the formula (Xa), (Xb) or (Xc) respectively: where each of the asterisks (*) in the formula represents a final group that may or may not vary between different polypharnesene polymer molecules depending on many factors such as the molar ratio of the starting materials, the presence or absence of a chain of a terminating agent, and the state of a particular polymerization process at the end of the polymerization step.

In some embodiments, the X and Y of the formula (X ') or (Xa) are joined in a substantially linear form. In other embodiments, the X and Y of the formula (X ') or (Xa) are linked in a substantially branched form. In other embodiments, the X and Y of the formula (X ') or (Xa) are joined in a substantially star-shaped manner. In still other embodiments, each of the X's and Y's independently form at least one block along the polymer chain to thereby provide a diblock, a triblock or multiple block interpolymer having at least one block X and at least one Y block. In still other embodiments, X and Y are randomly distributed along the polymer chain to thereby provide a random farnesene interpolymer. In still other modalities, the X and the Y are distributed from alternatively along the polymer chain to thereby provide an alternate farnesin interpolymer.

In some embodiments, Xs, Ys and Zs of the formula (X ") or (Xb) are linked in a substantially linear manner In other embodiments, Xs, Ys and Zs of the formula (X") or (Xb) are linked substantially in branched form. In other embodiments, Xs, Ys and Zs of the formula (X ") or (Xb) are substantially linked in a star form.In still other embodiments, each of Xs, Ys and Zs independently forms at least one block along of the polymer chain in order to provide a tri-block or multi-block farnesene interpolymer having at least one block X and at least one block Y, at least one block Z. In still other embodiments, Xs, Ys and Zs are distributed randomly along the polymer chain to provide a random farnesene interpolymer.In still other embodiments, Xs, Ys and Zs are alternatively distributed along the polymer chain to provide an alternate farnesin interpolymer. .

In some embodiments, Xs, Ys, Zs and Qs of the formula (X '' ') or (Xc) are linked in a substantially linear manner. In other embodiments, Xs, Ys, Zs and Qs of the formula (X '' ') or (Xc) are substantially branched. In other embodiments, Xs, Ys, Zs and Qs of the formula (X '' ') or (Xc) are substantially linked in the form of star. In yet other embodiments, each of Xs, Ys, Zs and Qs independently forms at least one block along the polymer chain to provide a tetra-block or multi-block farnesene interpolymer having at least one block X , at least one block Y, at least one block Z, and at least one block Q. In still other embodiments, Xs, Ys, Zs and Qs are distributed randomly along the polymer chain to provide an interpolymer of random farneseno. In still other embodiments, Xs, Ys, Zs and Qs are alternatively distributed along the polymer chain to provide an alternate farnesin interpolymer.

In some embodiments, the amount of farnesene in the farnesin interpolymer described herein is greater than about 1.5 mole%, greater than about 2.0 mole%, greater than about 2.5 mole%, greater than about 5%. % by mole, greater than about 10% by mole, greater than about 15% by mole, greater than about 20% by mole, greater than about 21% by mole, greater than about 22% by mole, higher about 23% by mole, greater than about 24% by mole, greater than about 25% by mole, or greater than about 30% by mole, based on the total amount of the farnesin interpolymer. In other embodiments, the amount of farnesene in the farnesin interpolymer described in present is less than about 90% by moles, less than about 80% by moles, less than about 70% by moles, less than about 60% by moles, less than about 50% by moles, less than about of 40% by moles, or less than about 30% by moles, based on the total amount of the farnesin interpolymer.

In some embodiments, the amount of the vinyl monomer of the farnesin interpolymer described herein is greater than about 1.5%, greater than about 2.0%, greater than about 2.5%, greater than about 5%, greater than about 10%, greater than about 15%, or greater than about 20%, based on the moles or total weight of the farnesin interpolymer. In other embodiments, the amount of the vinyl monomer (s) of the farnesin interpolymer described herein is less than about 90%, less than about 80%, less than about 70%, less than about 60%, less than about about 50%, less than about 40%, or less than about 30%, based on the moles or total weight of the farnesin interpolymer. In other embodiments, the amount of the vinyl monomer (s) in the farnesin interpolymer described herein is less than about 1% to about 90%, from about 5% to about 80%, of about 10% to around 70%, from around 10% to around 60%, from around 10% to around 50%, from around 10% to around 40%, or from 10% to around 30%, based on the moles or total weight of the farnesin interpolymer.

In certain embodiments, the mole percent ratio of farnesene to at least one vinyl monomer (ie, the ratio of the mole percent of X to Y, or X to the sum of Y, yz, X or the sum of Y , Z and Q) in the farnesin interpolymer described herein is from about 1: 5 to about 100: 1. In other embodiments, the ratio of X to Y, or X mole percent to the sum of Y, and z, X or to the sum of Y, Z and Q is from about 1: 4 to about 100: 1; from around 1: 3.5 to around 100: 1, from around 1: 3 to around 100: 1, from around 1: 2.5 to around 100: 1, or from around 1: 2 to around 100 :1. In some embodiments, m is 1 or greater, the ratio of the molar percentage of X to Y, or X to the sum of Y, yz, X or to the sum of Y, Z and Q is about 1: 4 to about 100: 1 In certain embodiments, the amount of the formula (? ') In the polyfarnesene described herein is greater than about 85% by weight, greater than about 80% by weight, greater than about 70% by weight, greater than about 60% by weight, or greater than about 50% by weight, based on the total weight of polyfarnesene. In other embodiments, the amount of the formula (III ') in the polyfarnesene described herein is at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 40% by weight, at least about 50% by weight weight, at least about 60% by weight, at least about 70% by weight, at least about 75% by weight, at least about 80% by weight, at least about 85% by weight, at least about of 90% by weight, at least about 95% by weight, or at least about 99% by weight, based on the total weight of polyfarnesene. In other embodiments, the amount of the formula (II ') in the polyfarnesene described herein is from about 1% by weight to about 99% by weight, from about 5% by weight to about 99% by weight , from about 10% by weight to about 99% by weight, or from about 15% by weight to about 99% by weight, based on the total weight of polyfarnesene. In still other embodiments, the amount of formula (IV) in the polyfarnesene described herein is greater than about 0.1% by weight, greater than about 0.5% by weight, greater than about 1% by weight, greater than about 2% by weight, or greater than about 3% by weight, based on the total weight of polyfarnesene. In some embodiments, the polyfarnesene described herein is substantially free of the formula (? '), (II'), (??? ') or (IV).

In certain modalities, the amount of the formula (V), (VI '), (VII') u (VIII ') in the polyfarnesene described herein is greater than about 1% by weight, greater than about 5% by weight, greater than about 10% by weight, greater than about 20% by weight, greater than about 30% by weight, greater than about 40% by weight, greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, or greater than about 90% by weight, based on the total weight of polyfarnesene. In other embodiments, the amount of formula (V), (VI '), (VII') or (VIII ') in the polyfarnesene described herein is at least about 1% by weight, at least about 2% by weight, at least about 3% by weight, at least about 5% by weight, at least about 10% by weight, at least about 20% by weight, at least about 30% by weight, at least about 40% by weight, at least about 50% by weight, at least about 60% by weight, based on the total weight of polyfarnesene. In other embodiments, the amount of the formula (V), (VI '), (VII') or (VIII ') in the polyfarnesene described herein is from about 1% by weight to about 99% by weight, from about 5% by weight to about 99% by weight, from about 10% by weight to about 99% by weight, or from about 15% by weight to about 99% by weight, based on the weight total of polyfarnesene. In some modalities, polyfarnesene described herein is substantially free of formula (V), (VI '), (VII') u (VIII ').

Any compound containing a vinyl group, i.e., -CH = CH 2, which is copolymerizable with farnesene can be used as a vinyl monomer to make the farnesene interpolymer described herein. Useful vinyl monomers described herein include ethylene, ie, CH2 = CH2. In certain embodiments, the vinyl monomer has the formula (XV): wherein each of R5, R6, R7 and R8 is independently H, an organyl group or a functional group.

In some embodiments, at least one of R5, R6, R7 and R8 of the formula (IX), (IX ') or (XV) is an organyl group. In other embodiments, the organo group is a hydrocarbyl, a substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, a heterocyclyl or a substituted heterocyclyl. In certain embodiments, each of R5, R6, R7 and R8 of the formula (IX), (IX ') or (XV) is independently H, alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl, alkynyl, heterocyclyl, (e.g. , pyridyl), alkoxy, aryloxy, carboxy (i.e., -COOH), alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n- butoxycarbonyl), aminoalkoxycarbonyl (e.g., 2-aminoethoxycarbonyl), hydroxyalkoxycarbonyl (e.g., 2-hydroxyethoxycarbonyl), aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy (e.g., CH3-C (= 0) -0), nitrile or halo (eg example, F, Cl, Br and I). In certain embodiments, R 5 of the formula (IX), (IX ') or (XV) is aryl; and each of R6, R7 and R8 is H. In other embodiments, R5 of the formula (IX), (IX ') or (XV) is phenyl; and each of R6, R7 and R8 is H. In some embodiments, R5 of the formula (IX), (IX ') or (XV) is carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy or nitrile; R7 is H or alkyl; and each of R6 and R8 is H. In other embodiments, R5 of the formula (IX), (IX ') or (XV) is carboxy or alkoxycarbonyl; R7 is alkyl; and each of R6 and R8 is H. In other embodiments, R5 of the formula (IX), (IX ') or (XV) is carboxy or alkoxycarbonyl; each of R6, R7 and R8 is H.

In certain embodiments, at least one of R5, R6, R7 and R8 of the formula (IX), (IX ') or (XV) is H. In other embodiments, each of R5, R6, R7 and R8 of the formula (IX), (IX ') or (XV) is H. In other embodiments, R5 of the formula (IX), (IX') or (XV) is hydrocarbyl; and each of R6, R7 and R8 is H. In still other embodiments, the hydrocarbyl is alkyl, cycloalkyl or aryl. In still other embodiments, none of R5, R6, R7 and R8 of the formula (IX), (IX ') or (XV) is either it comprises an alkenyl, a cycloalkenyl or an alkynyl. In still other embodiments, none of R5, R6, R7 and R8 of the formula (IX), (IX ') or (XV) is or comprises a hydrocarbyl, a substituted hydrocarbyl, a heterocyclyl or a substituted heterocyclyl.

In certain embodiments, at least one of R5, R6, R7 and R8 of the formula (IX), (IX ') or (XV) is a functional group containing a halo, O, N, S, P or a combination of the same. Some of the non-limiting examples to the appropriate functional groups include hydroxy, alkoxy, aryloxy, amino, nitro, thiol, thioether, imine, cyano, amido, phosphonate (-P (= 0) (O-alkyl) z, -P (= 0) (0-aryl) 2, or -P (= 0) (0-alkyl)) 0-aryl), phosphinate (-P (= 0) (0-alkyl) alkyl, -P (= 0) (0-aryl) alkyl, -P (= 0) (0-alkyl) aryl, or -P (= 0) (0-aryl) aryl), carboxyl, thiocarbonyl, sulfonyl (-S (= 0) 2alkyl, or -S (= 0) 2-aryl), sulfonamide (-S02NH2, S02NH (alkyl), -S02NH (aryl), -S02N (alkyl) 2, -S02N (aryl) 2, or -S02 (aryl) (alkyl)), Ketone, aldehyde, ester, oxo, amino (primary, secondary or tertiary), -C02CH3, -C0NH2, -0CH2C0NH2, -NH2, -0CHF2, -0CF3, -NH (alkyl), -N (alkyl) 2, -NH (aryl), -N (alkyl) (aryl), -N (aryl) 2, -CH0, -C0 (alkyl), -CO (aryl), -C02 (alkyl), or -C02 (aryl). In some embodiments, the functional group is or comprises alkoxy, aryloxy, carboxy, (i.e., -C00H), alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, n- propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl), aminoalkoxycarbonyl (e.g., 2-aminoethoxycarbonyl), hydroxyalkoxycarbonyl (e.g., 2-hydroxyethoxycarbonyl), aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy (e.g., CH3-C (= 0) -0) , nitrile or halo (for example, F, Cl, Br and I). In certain embodiments, the functional group is or comprises carboxy, alkoxycarbonyl, aminoalkoxycarbonyl, hydroxyalkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy or nitrile. In some embodiments, the functional group is or comprises carboxy or alkoxycarbonyl. In other embodiments, none of R5, R6, R7 and R8 of the formula (IX), (IX ') or (XV) is or comprises a functional group. In other embodiments, none of R5, R6, R7 and R8 of the formula (IX), (IX ') or (XV) is or comprises alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminoalkoxycarbonyl, hydroxyalkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy , nitrile or halo.

In some embodiments, the vinyl monomer is a substituted or unsubstituted olefin such as ethylene or styrene, vinyl halide (eg, vinyl chloride), vinyl ether, vinyl acetate, vinylpyridine, vinylidene fluoride, acrylonitrile, acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester, acrylamide, methacrylamide or a combination thereof. In others embodiments, styrene, vinyl halide, vinyl ether, vinyl acetate, vinylpyridine, vinylidene fluoride, acrylonitrile, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylamide or methacrylamide are unsubstituted. In certain embodiments, styrene, vinyl halide, vinyl ether, vinyl acetate, vinylpyridine, vinylidene fluoride, acrylonitrile, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylamide or methacrylamide are substituted. Some non-limiting examples of substituted styrene include 2-fluorostyrene, 4-fluorostyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-dimethylstyrene, 2-5. dimethylstyrene and combinations thereof.

In some embodiments, the vinyl monomer is a substituted or unsubstituted olefin such as ethylene or styrene, acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester, acrylamide, methacrylamide or a combination thereof. In certain embodiments, the vinyl monomer is a substituted or unsubstituted olefin such as styrene, acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester or a combination thereof. In other embodiments, the vinyl monomer is ethylene, an α-olefin or a combination thereof.

Some non-limiting examples of suitable α-olefins include styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene and combinations thereof .

In some embodiments, the vinyl monomer is an aryl such as styrene, α-methylstyrene, or divinylbenzene. Additional examples include functional vinyl aryls such as those described in U.S. Patent No. 7,041,761 which is incorporated herein by reference.

In some embodiments, the farnesin interpolymers described herein are derived to the minor of a farnesene and of at least one olefin monomer. An olefin refers to an unsaturated hydrocarbon base compound with at least one carbon-carbon double bond. In certain embodiments, the olefin is a mixture of dienes. Depending on the selection of catalysts, any olefin can be used in the embodiments of the invention. Some non-limiting examples of suitable olefins include C2-20 aliphatic compounds and C8-20 aromatics not containing vinyl saturation, as well as cyclic compounds, such as cyclobutene, cyclopentene, dicyclopentadiene and norbornene, including but not limited to, norbornene substituted in the 5 and 6 position with hydrocarbyl or cyclohydrocarbyl groups of Ci_2o- Other non-limiting examples to the Suitable olefins include mixtures of such olefins as well as mixtures of such olefins with diolefin compounds of C-40 · Some of the non-limiting examples of the appropriate olefin or the α-olefin monomers include styrene, ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene,, 6-dimethyl-1-heptene, 4-vinylcyclohexene, vinylcyclohexene, norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, dienes of 4-40 carbon atoms, and combinations thereof. In certain embodiments, the olefin monomer is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or a combination thereof. In some embodiments, the dienes of 4-40 carbon atoms include, but are not limited to, 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene. , 1, 9-decadiene, isoprene, myrcene, other IO-olefins of 4-40 carbon atoms and combinations thereof.

In some embodiments, the farnesene interpolymers described herein are derived from at least one farnesene and a vinyl monomer selected from styrene, substituted styrene, dienes of 4-40 carbon atoms, vinyl halides, vinyl ether, vinyl acetate, vinylpyridine, vinylidene fluoride, acrylonitrile, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, acrylamide and methacrylamide. In certain embodiments, the farnesin interpolymers described herein are derived from at least one farnesene and a methacrylic ester such as methyl methacrylate, stearyl methacrylate, lauryl methacrylate, isodecyl methacrylate, a hydroxyalkyl methacrylate (e.g., methacrylate) of 2-hydroxyethyl), or an aminoalkyl methacrylate (e.g., 2-aminoethyl methacrylate, 2- (dimethylamino) ethyl methacrylate, and 2- (diethylamino) ethyl methacrylate). In certain embodiments, the farnesin interpolymers described herein are derived from at least one farnesene and an acrylic ester such as methyl acrylate, ethyl acrylate, butyl acrylate, a hydroxyalkyl acrylate (e.g., 2-hydroxyethyl acrylate) ), or an aminoalkyl acrylate (e.g., 2-aminoethyl acrylate, 2- (dimethylamino) ethyl acrylate, and 2- (diethylamino) ethyl acrylate). In certain embodiments, the farnesin interpolymers described herein are derived from at least one farnesene and vinyl acetate. In certain embodiments, the farnesin interpolymers described herein are derived from at least one farnesene and acrylic acid. In certain modalities, interpolymers of farnesene described herein are derived from at least one farnesene and methacrylic acid.

In some embodiments, the farnesin interpolymers described herein are derived from at least one farnesene and two vinyl monomers selected from styrene, substituted styrene, dienes of 4-40 carbon atoms, vinyl halides, vinyl ether, vinyl acetate, vinylpyridine, vinylidene fluoride, acrylonitrile, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, acrylamide, methacrylamide and combinations thereof. In certain embodiments, the farnesin interpolymers described herein are derived from at least one farnesene and two methacrylic esters (e.g., methyl methacrylate, 2-hydroxyethyl methacrylate, stearyl methacrylate, lauryl methacrylate and isodecyl methacrylate). In certain embodiments, the farnesin interpolymers described herein are derived from at least one farnesene and two acrylic esters, (e.g., methyl acrylate, ethyl acrylate and butyl acrylate). In certain embodiments, the farnesin interpolymers described herein are derived from at least one farnesene, a methacrylic ester and an acrylic ester. In certain embodiments, the farnesene interpolymers described herein are derived from at least one farnesene, a methacrylic ester or an acrylic ester, and acid acrylic or methacrylic acid. In certain embodiments, the farnesin interpolymers described herein are derived from at least one farnesene, styrene and acrylonitrile.

In some embodiments, the farnesin interpolymers described herein are derived from at least one farnesene and three vinyl monomers selected from styrene, substituted styrene, dienes of 4-40 carbon atoms, vinyl halides, vinyl ether, vinyl acetate, vinylpyridine, vinylidene fluoride, acrylonitrile, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, acrylamide, methacrylamide and combinations thereof.

Some non-limiting examples of dienes of 4-40 carbon atoms include isoprene, butadiene and myrcene). Some non-limiting examples of substituted styrene include 2-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 4-ethylstyrene, 2,4-dimethylstyrene and 4-fluorostyrene. Some non-limiting examples of vinyl halides include vinyl chloride and vinylidene fluoride.

The farnesin interpolymers described herein may be derived from a farnesene and a styrene. The farnesene interpolymers may further comprise at least one olefin of 2-20 carbon atoms, at least one diolefin of 4-18 carbon atoms, at least one alkylbenzene or a combination thereof. Unsaturated comonomers suitable for polymerizing with the farnesene include, for example, ethylenically unsaturated monomers, polyenes such as d or und dienes, alkylbenzenes, and the like. Examples of such comonomers include ethylene, olefins of 2-20 carbon atoms such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1- octene, 1-nonene, 1-decene, and the like. Other suitable monomers include styrene, halo- or alkyl substituents, vinylbenzene cyclobutane, 1,4-hexadiene, 1-octanediene, and cycloalkenes such as cyclopentene, cyclohexene and cyclooctene.

Some suitable und diene monomers can be in a straight chain, in a branched chain or a cyclic hydrocarbon diene having from 6 to 15 carbon atoms. Some of the non-limiting examples to the appropriate dienes include the straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as 5-methyl-1, -hexadiene; 3,7-dimethyl-1,6-octadiene; 3, -dimethyl-l, 7-octadiene and d isomers of dihydromyricin and dihydroquinine, single-ring alicyclic dienes, such as 1,3-cyclopentadiene; 1 ^ 4-cyclohexadiene; 1, 5-cyclooctadiene and 1,5-cyclododecadiene, and acyclic fused multiple ring and ring bridged dienes, such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo- (2, 2, 1) -hepta-2, 5-diene; alkenyl, alkylidino, cycloalkenyl and cycloalkylidino norbornenes, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene. Of the dienes typically used to prepare EPDM, the particularly preferred dienes are 1-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene- 2-norbornene (MNB), and dicyclopentadiene (DCPD). In certain embodiments, the diene is 5-ethylidene-2-norbornene (ENB) or 1,4-hexadiene (HD). In other embodiments, the farnesin interpolymers are not derived from a polyene such as dienes, trienes, tetraenes, and the like.

In some embodiments, the farnesin interpolymers are interpolymers of farnesene, styrene and an olefin of 2-20 carbon atoms. Some non-limiting examples of suitable olefins include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. In some embodiments, the farnesin interpolymers described herein are not derived from ethylene. In some embodiments, the farnesin interpolymers described herein are not derived from one or more olefins of 2-20 carbon atoms.

In certain embodiments, the vinyl monomer does not It comprises a terpene. In other embodiments, the vinyl monomer does not comprise a terpene selected from isoprene, dipentene, α-pinene, β-pinene, terpinolene, limonene (dipentene), terpinene, tujeno, sabinene, 3-carene, camphene, cadinone, caryophyllene, myrcene, ocimene, cedrene, bisalbono, bisalbono, bisalbono, zingiberene, humulene, citronellol, linalool, geraniol, nerol, ipsenol, terpineol, D-terpineol- (4), dihydrocarveol, nerolidol, farnesol, eudesmol, citral, D-citronellal, carvone, D-pulegone, piperitone, carvenone, bisabolena, selineno, santaleno, a vitamin A, abietic acid or a combination thereof. In other embodiments, the vinyl monomer does not comprise an isoprene.

The farnesin interpolymers can be functionalized by incorporating at least one functional group into their polymer structure. Exemplary functional groups may include, for example, mono- and difunctional ethylenically unsaturated carboxylic acids, mono- and difunctional ethylenically unsaturated carboxylic acid anhydrides, salts thereof and esters thereof. Such functional groups can be inserted into the farnesin interpolymers, or can be copolymerized with farnesene with an optional additional comonomer, to form a farnesin interpolymer, the functional comonomer and other optional comonomers. Any person skilled in the art can use any means to graft groups functional A particularly useful group or comonomer is maleic anhydride. In some embodiments, the farnesin interpolymers are interpolymers of farnesene and a functional comonomer such as maleic anhydride. In certain embodiments, the farnesin interpolymers are interpolymers of farnesene, a functional comonomer such as maleic anhydride and a vinyl monomer comprising styrene, acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester or a combination thereof.

Any compound having at least one double bond and at least one functional group described herein can be used as a functional comonomer to prepare the farnesne interpolymers described herein. In some embodiments, the functional comonomer has the formula (XVI), (XVII), (XVIII), (XIX) or (XX): where each of Q1 and Q6 is independently 0, S, NR23 or N-Q7; each of Q2, Q3, Q4 and Q5 is independently halo, Q8, NR24R25, OR26 or 0-Q8; Q7 and Q8, respectively, have the following formulas: where k is an integer from 1 to about 10; and Q is OH, NH2, NHR30, carboxyl, epoxy or glycidyl; Y each of R9 to R30 is independently H, alkyl of 1-20 carbon atoms, alkenyl of 1-20 carbon atoms, alkynyl of 1-20 carbon atoms, cycloalkyl, aryl, aralkyl, alkaryl, OH, N¾, carboxyl , epoxy or glycidyl, or R19 and R22 together form a group - (CH2) ra- wherein m is an integer from 1 to about 6, and wherein each of the alkyl of 1-20 carbon atoms, alkenyl of 1-20 carbon atoms, alkynyl of 1-20 carbon atoms, cycloalkyl, aryl, aralkyl, alkaryl, epoxy, glycidyl and - (CH2) m- is optionally substituted.

In certain embodiments, the functional comonomer has the formula (XVI). Some non-limiting examples of the functional comonomer having the formula (XVI) include, maleimide, maleic anhydride, citraconic anhydride, itaconic anhydride and combinations thereof.

In some embodiments, the functional comonomer has the formula (XVII). Some non-limiting examples of the functional comonomer having the formula (XVII) include mesaconic acid, maleic acid, fumaric acid, malenyl chloride, monomethyl maleate, dimethyl maleate, glycidyl maleate, dipropyl maleate, diisobutyl maleate, dihexyl maleate, dibenzyl maleate, p-chlorophenylmethyl maleate, phenylethyl maleate , dicyclopentyl maleate and combinations thereof.

In certain embodiments, the functional comonomer has the formula (XVIII). Some non-limiting examples of the functional comonomer having the formula (XVIII) include methacrylic acid, acrylic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate, methacrylate 4-hydroxybutyl, adduct of caprolactone of 2-hydroxyethyl methacrylate, adduct of ethylene oxide of 2-hydroxyethyl methacrylate, adduct of propylene oxide of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate caprolactone adduct, 2-hydroxyethyl acrylate ethylene oxide adduct, 2-acrylate propylene oxide adduct hydroxyethyl, 2-hydroxyethyl crotonate, 2-hydroxypropyl crotonate, 3-hydroxypropyl crotonate, 3-hydroxybutyl crotonate, 4-hydroxybutyl crotonate, 5-hydroxypentyl crotonate, 6-hydroxyhexyl rotonate, methacrylate glycidyl, glycidyl acrylate, glycidyl ethacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate and combinations thereof.

In some embodiments, the functional comonomer has the formula (XIX). Some non-limiting examples of the functional comonomer having the formula (XIX) include allyl alcohol, hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyl ethyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyheptyl vinyl ether, hydroxycyclohexyl vinyl ether, allyl glycidyl ether, p-glycidyloxystyrene, p-glycidyloxy-a-methylstyrene, p- (3, 4-epoxycyclohexylmethyloxy) styrene, p- (3, -epoxycyclohexylmethyloxy) -a-methylstyrene, glycidylethylene, 3-epoxycyclohexylmethylethylene, glycidylvinylether, 3,4-epoxycyclohexylmethylvinylether, 3,4-epoxycyclohexylmethylaleyl ether and combinations thereof.

In certain embodiments, the functional comonomer has the formula (XX). Some non-limiting examples of the functional comonomer having the formula (XX) include bicyclo [2, 2, 2] -oct-5-en-2,3-dicarboxylic acid anhydride, bicyclo acid anhydride [2, 2, 1] hept-5-en-2, 3-dicarboxylic and combinations thereof.

In some embodiments, the farnesin interpolymers are farnesin interpolymers, at least one vinyl monomer described herein and at least one functional comonomer described herein by copolymerizing farnesene, at least one vinyl monomer and at least one functional comonomer in the presence of a catalyst or initiator described herein. In certain embodiments, the farnesin interpolymers are farnesin interpolymers, at least two different vinyl monomers described herein and at least one functional comonomer as described herein by copolymerizing farnesene, at least two different vinyl monomers and at least one functional comonomer in the presence of a catalyst or initiator described herein. The amount of each farnesene, vinyl monomer and functional comonomer in the farnesin interpolymers is as described herein.

The amount of the functional group present in the functionalized farnesene interpolymer can vary. In some embodiments, the functional group or comonomer is present in an amount of at least about 1.0% by weight, at least about 2.5% by weight, at least about 5% by weight, at least about 7.5% by weight , or at least about 10% by weight, based on the total weight of the farnesin interpolymer. In other embodiments, the functional group is present in an amount less than about 40% by weight, less than about 30% by weight, less than about 25% by weight, less than about 20% by weight, or less than about 15% by weight, based on the total weight of the farnesin interpolymer.

Any catalyst that can polymerize or copolymerize farnesene can be used to make the polyphosphenes described herein. Some of the non-limiting examples of suitable catalysts include organolithium reagents, Ziegler-Natta catalysts, Kaminsky catalysts and other metallocene catalysts. In some embodiments, the catalyst is a Ziegler-Natta catalyst, a Kaminsky catalyst, a metallocene catalyst or a combination thereof. Other catalysts or initiators that can be polymerized or copolymerized farnesene can also be used to make the polyphosphenes described herein. Some non-limiting examples of other catalysts or initiators include catalysts or free radical initiators, cationic catalysts or initiators, and anionic catalysts or initiators.

In some embodiments, the catalyst further comprises a co-catalyst. In other embodiments, the co-catalyst is a hydride, an alkyl or an aryl of a metal or a combination thereof. In still other modalities, the metal is aluminum, lithium, zinc, tin, cadmium, beryllium or magnesium.

In some embodiments, the catalyst is an organolithium reagent. Any organolithium reagent that can act as a catalyst to polymerize olefins can be used. Some of the non-limiting examples to the appropriate organolithium reagents include n-butyllithium, sec-butyllithium or tert-butyllithium. Some of the non-limiting examples to the appropriate Lewis bases include TMEDA, PMDTA or esparteine. Some of the organolithium reagents are described in Zvi Rappoport et al., "The Chemistry of Organolithium Compounds", Part 1 (2004) and Vol. 2 (2006), both incorporated herein by reference.

In some embodiments, the catalyst is a mixture of an organolithium reagent and a Lewis base. Any Lewis base that can degrade the organolithium reagents, making them more soluble and more reactive, can be used herein. An aggregate organolithium reagent generally has a lithium that coordinates more than one carbon atom and one carbon that coordinates more than one lithium atom. Some of the non-limiting examples to the appropriate Lewis bases include 1, 2-bis (dimethylamino) ethane (also known as tetramethylethylenediamine or TMEDA),?,?,? ,? ' , N "-pentamethyldiethylenetriamine (PMDTA), esparteine and combinations thereof.

In some modalities, the catalyst is a Ziegler-Natta catalyst. Generally, Ziegler-Natta catalysts can be heterogeneous or homogeneous. In some embodiments, the Ziegler-Natta catalyst used to polymerize the polypharmames described herein is a heterogeneous Ziegler-Natta catalyst. Some useful Ziegler-Natta catalysts are described in J. Boor, "Ziegler-Natta Catalysts and Polymerizations", Saunders College Publishing, p. 1-687 (1979); and Malcolm P. Stevens, "Polymer Chemistry, an Introduction" Third Edition, Oxford University Press, pp. 236-245 (1999), both incorporated herein by reference.

The heterogeneous Ziegler-Natta catalysts generally comprise (1) a metal transition compound comprising an element of groups IV to VIII; and (2) an organometallic compound comprising a metal of groups I to III of the periodic table. The transition metal compound is related as the catalyst while the organometallic compound is related as the co-catalyst or the activator. The transition metal compound generally comprises a metal and one or more anions and ligands. Some of the non-limiting examples of suitable metals include titanium, vanadium, chromium, molybdenum, zirconium, iron and cobalt. Some of the non-limiting examples of suitable anions or ligands include halides, oxyhalides, alkoxy, acetylacetonyl, cyclopentadienyl and phenyl. Some other non-limiting examples of suitable anions or ligands include sulfides, oxides, oxychlorides, dialkylamino, alkoxy, alkylthio, acetylacetonate, arenos, cyclopentadienyl, indenyl, nitroso, halide (eg, CI, Br, I or F), phosphate, chromate, sulfate, carboxylates, carbon monoxide or a combination of the same. Some non-limiting examples of the suitable transition metal compound include CoCl2, TiCl3, TiCl4, Til4, Ti (OR) 4, where R is alkyl, VC13, VOCl3, VC14, ZrCl4, Ti (OC6H9) 4, and Cr (C6H5CN) 6 In some embodiments, one or more electron donors such as amines, ethers and phosphines can be added to the Ziegler-Natta catalyst to increase activity.

Some other non-limiting examples of suitable transition metal compounds include TiCl 2, TiBr 3, Til 3, ZrCl 2, CrCl 2, TiCl (Oi-Pr) 3, CrCl 3, NbCl 5, VO (OET) Cl 2, VO (OET) 2 Cl, VO (OET) ) 3, V (acac) 3, FeCl2, FeBr2, Fe (acac) 2, Cp2TiCl2, Cp2Ti (alkyl) Cl, Cp2Ti (C6H5) 2, Co (acac) 3, Ti (0Pr) 4, Cr (acac) 3 , VC13-3THF, Cr (CO) 6, Mo02 (acac) 2, Mo02 (acac) 3, Mo02 (alkoxy) 2, To (NEt2) 4 and combinations thereof. Some additional non-limiting examples of suitable transition metal compounds include Zr (Ot-Bu) 4, ZrBz4, CrCl3 (THF) 3, Ni (dppe) Cl2, Ni (COD) 2, Pd (OAc) 2, C0 (dppe ) Cl2, Fe (acac) 3, TiCl3 (THF) 3, Me2Si (Cp) 2ZrCl2, EBTHIZrCl2, Co (acac) 3, Nd (N (SiMe3) 2) 3, TiCl4 / VOCl3, Zr (OEt) 4, ZrCl4 (THF) 2 and combinations thereof.

Any co-catalyst or activator that can ionize the organometallic complex to produce an active olefin polymerization catalyst can be used herein. Generally, organometallic co-catalysts are hydrides, alkyls or aryls of metals, such as aluminum, lithium, zinc, tin, cadmium, beryllium and magnesium. Some of the non-limiting examples to the appropriate co-catalysts include alumoxanes (methylalumoxane (MAO), PMAO, ethylalumoxane, diisobutylalumoxane), alkylaluminum compounds having the formula AIR3 where R is alkyl (eg, trimethylaluminum, triethylaluminum, diethylaluminum chloride , trimethylaluminum, triisobutylaluminum, trioctylaluminum), diethylzinc, di (i-butyl) zinc, di (n-hexyl) zinc, and ethylzinc (t-butoxide) and the like. Other suitable co-catalysts include acid salts containing non-nucleophilic anions. These compounds generally consist of coarse ligands bound to boron or aluminum. Some of the non-limiting examples of such compounds include tetrakis (pentafluorophenyl) borate lithium, tetrakis (pentafluorophenyl) lithium aluminate, tetrakis (pentafluorophenyl) borate anilinium and the like. Some of the non-limiting examples to the appropriate co-catalysts also include organoboranes, which include boron and one or more alkyl, aryl or aralkyl groups. Others non-limiting examples to the appropriate co-catalysts include substituted or unsubstituted trialkyl and triarylborane such as tris (pentafluorophenyl) borane, triphenylborane, tri-n-octylborane and the like. These and other suitable co-catalysts containing boron or activators are described in U.S. Patent Nos. 5,153,157, 5,198,401, and 5,241,025, both incorporated herein by reference.

In certain embodiments, the Ziegler-Natta catalyst can be impregnated with a support material. Some suitable support materials are described in Malcolm P. Stevens, "Polymer Chemistry, an Introduction" Third Edition, Oxford University Press, p. 251 (1999), which are incorporated herein by reference.

The support material is generally an inert or substantially inert material to the olefin polymerization reactions. Non-limiting examples to the appropriate support materials include MgCl2, MgO, alumina such as activated alumina and microgel alumina, silica, magnesia, diatomaceous earth, fuller earth, clays, alumina silicas, halides and porous rare earth oxyhalides, and combinations thereof. The support material can have a surface area between about 5 m2 / g and about 450 m2 / g, as determined by the BET (Brunauer-Emmet-Teller) method of surface measurement, as described S. Brunauer, P. H. Emmett, and E. Teller, Journal of the United States Chemical Society, 60, 309 (1938), which is incorporated herein by reference. In some embodiments, the surface area of the support material is between about 10 m2 / g to about 350 m2 / g. In other embodiments, the surface area of the support material is between about 25 m2 / g to about 300 m2 / g.

The support material may have an average particle size of from about 20 to about 300 microns, from about 20 to about 250 micrometers, from about 20 to about 200 micrometers, from about 20 to about 150 micrometers, from about 20 to about 120 micrometers, from about 30 to about 100 micrometers , or from around 30 to about 90 micrometers. The apparent compacted or consolidated density of the support material can vary between about 0.6 and about 1.6 g / cc, between about 0.7 and about 1.5 g / cc, between about 0.8 and about 1.4 g / cc, or between about 0.9 and about 1.3 g / cc.

In certain embodiments, the catalyst used herein is or comprises a Kaminsky catalyst, also known as a homogeneous Ziegler-Natta catalyst. The Kaminsky catalyst can be used to produce polyolefins such as the polypharmames described herein with unique physical properties and structures. Some Kaminsky catalysts or homogeneous Ziegler-Natta catalysts are described in Malcolm P. Stevens, "Polymer Chemistry, an Introduction" Third Edition, Oxford University Press, pp. 245-251 (1999); and John Scheirs and Walter Kaminsky, "Metallocene-Based Polyolefins: Preparatlon, Properties, and Technology" Volume 1, Wiley (2000), both incorporated herein by reference.

In some embodiments, a co-catalyst is used with the Kaminsky catalyst. The co-catalyst can be any co-catalyst described herein. Some Kaminsky catalysts and co-catalysts are described in U.S. Patent 7,655,739, which is incorporated herein by reference.

In certain embodiments, the catalyst for making the farnesin interpolymer described herein is or comprises a metallocene catalyst. Some metallocene catalysts are described in Tae Oan Ahn et al., "Modification of a Ziegler-Natta catalyst with a metallocene catalyst and its olefin polymerization behavior", Engineering and Science of Polymers, 39 (7), p. 1257 (1999); and John Scheirs and Walter Kaminsky, "Metallocene-Based Polyolefins: Preparation, Properties, and Technology" Volume 1, Wiley (2000), and Patent of the United States No. 7,655,739 all of which are incorporated herein by reference.

In some embodiments, the catalyst or initiator is a free radical catalyst or initiator. Any free radical initiator that can act as an initiator to polymerize olefins can be used herein. Some free radical initiators are described in Denisov et al., "Handbook of Free Radical Initiators", iley-Interscience, pp. 1-904 (2003), which are incorporated herein by reference. Non-limiting examples of suitable free radical initiators include hydrogen peroxide, hydroperoxides, dialkylperoxides, diacylperoxides, peroxyesters, peroxy ketones, azo compounds, organic poloxides, photoinitiators, persulfates and combinations thereof.

Any azo compound that can act as an initiator to polymerize olefins can be used herein. Non-limiting examples of suitable azo compounds include azobisisobutyronitrile, l, 1-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-amidinopropan) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid) and combinations thereof. Some non-limiting examples of available commercial azo compounds include VAZO® 52, 56, 64, 67, 68 and 88, all which can be obtained from DuPont, Wilmington, Delaware.

Any hydroperoxide that can act as an initiator for polymerizing olefins can be used herein. Some non-limiting examples of suitable hydroperoxides include eumeno hydroperoxide, t-butyl hydrogen peroxide, t-amyl hydrogen peroxide, and combinations thereof.

Any dialkylperoxide that can act as an initiator to polymerize olefins can be used herein. Some non-limiting examples of suitable dialkylperoxides include dicumyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, diisopropyl peroxide, di (2-t-butylperoxyisopropyl) benzene, 1,1-di (tert-butylperoxy) cyclohexane 3, 3, 5-trimethyl, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and combinations thereof.

Any diacyl peroxide that can act as an initiator to polymerize olefins can be used herein. Some non-limiting examples of suitable diacyl peroxides include benzoyl peroxide, acetylperoxide, lauroyl peroxide and combinations thereof.

Any peroxyester that can act as an initiator to polymerize olefins can be used herein. Some non-limiting examples of peroxyesters suitable include tert-butyl peroxyacetate, ethyl peroxybenzoate and combinations thereof.

Any organic polyoxide that can act as an initiator to polymerize olefins can be used herein. Some non-limiting examples of suitable organic polyoxides include dialkyl trioxides, hydrotrusoxides, tetroxides, and combinations thereof.

Any photoinitiator that can act as an initiator for polymerizing olefins can be used herein. Some non-limiting examples of suitable photoinitiators include acetophenone compounds, benzyl and benzoin compounds, benzophenones, thioxanthones, quinone compounds, cationic photoinitiators and combinations thereof.

Some non-limiting examples of suitable acetophenones include 2-benzyl-2- (dimethylamino) - 'morpholinbutyrophenone, 2-hydroxy-2-methylpropiophenone, 4'-ethoxyacetophenone, 4'-tert-butyl-2', 6'-dimethylacetophenone, , 2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4'-hydroxyacetophenone, 4'-phenoxyacetophenone and combinations thereof.

Some non-limiting examples of suitable benzyl and benzoin compounds include benzyl, 4,4-dimethylbenzyl, benzoin, benzoin ethyl ether, benzoin methylether, 4,4'-dimethoxybenzoin and combinations thereof. same.

Some non-limiting examples of suitable benzophenones include, 4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, benzophenone, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, 4-benzoylbiphenyl , 4, 4 '-bis [2- (1-propenyl) phenoxy] benzophenone, 4 (diethylamino) benzophenone, 4,4'-dihydroxybenzophenone, 4- (dimethylamino), phenophenone, 3,4-dimethylbenzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, methylbenzoylformate and combinations of the same.

Some non-limiting examples of suitable thioxanthones include thioxanthen-9-one, l-chloro-4-propoxy-9h-thioxanthen-9-one, 2-chlorothioxant-9-one, 2, -diethyl-9H-thioxanthen-9-one , isopropyl-9H-thioxanthen-9-one, 10-methylphenothiazine and combinations thereof.

Some non-limiting examples of suitable quinone compounds include 9, 10-phenanthrenequinone, 2-tert-butylanthraquinone, camphorquinone, anthraquinone-2-sulfonic acid, sodium salt and combinations thereof.

Some non-limiting examples of suitable persulfates (eg, peroxomonosulfates and peroxodisulfates) include ammonium persulfates (peroxomonosulfate or ammonium peroxodisulfate), potassium persulfates (peroxomonosulfate or potassium peroxodisulfate), sodium persulfates (peroxomonosulfate or sodium peroxodisulfate), and combinations thereof.

Some non-limiting examples of suitable cationic photoinitiators include bis (4-tert-butylphenyl) iodonium triflate, 4-bromophenyl) diphenylsulfonium triflate, (4-tert-butylphenyl) diphenylsulfonium triflate, diphenyliodonium hexafluorophosphate, diphenyliodonium nitrate, perfluoro diphenyliodonium-l-butansulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium triflate, (4-fluorophenyl) diphenylsulfonium triflate, N-hydroxynaphthalimide triflate, (4-iodophenyl) diphenylsulfonium triflate, (4-methoxyphenyl) diphenylsulfonium triflate, triflute of (4-methylphenyl) diphenylsulfonium, triflate of 1-naphthyldiphenylsulfonium, triflate of (4-phenoxyphenyl) diphenylsulfonium, triflate of (4-phenylthiophenyl) diphenylsulfonium, triflate of perfluoro-1-butansufonate of triphenyl sulfonium, triflate of tris (4-ter) -butylphenyl) sulfonium and combinations thereof.

In some embodiments, free radicals are generated by chemical processes such as thermal decomposition, photolysis, and redox reactions, all of which involve one or more of the free radical initiators described herein. In certain modalities, free radicals are generated by a process, such as ionizing radiation (eg, -, ß-,? -, or X-rays), electrolysis, and ultrasound, all of which do not involve any free radical initiator. In other embodiments, free radicals are generated by thermal decomposition, photolysis, ionizing radiation, redox reactions, electrolysis, ultrasound or a combination thereof.

In certain embodiments, free radicals are generated by thermal decomposition, where the initiator (eg, hydrogen peroxide, hydroperoxides, dialkylperoxides, diacylperoxides, peroxyesters, peroxy ketones, azo compound organic and poloxides) is heated until one or more bonds ( for example, bonds 0-0 or 0-N) are broken to produce one or more radicals. In some embodiments, the temperature of thermal decomposition is above about 20 ° C, above about 30 ° C, above about 40 ° C, above about 50 ° C, above about 60 ° C, above about 70 ° C, above about 80 ° C, above about 90 ° C or above about 100 ° C.

In some embodiments, free radicals are generated by photolysis where the initiator (e.g., azo compounds) is irradiated with radiation until one or more bonds (e.g., O-N bonds) are broken for produce one or more radicals. In certain embodiments, the radiation is visible light, ultraviolet light, X-rays, gamma rays or a combination thereof. In some embodiments, the temperature of the photolysis is below about 50 ° C, below about 40 ° C, below about 30 ° C, below about 20 ° C, below around 10 ° C or below around 0 ° C.

In certain embodiments, free radicals are generated by redox reactions where an initiator of oxidative free radicals (e.g., hydrogen peroxide, hydroperoxides, dialkyl peroxides, and diacylperoxides) are reduced by an organic reducing agent (e.g., diethylaniline, hydrazine, oxalic, formic acid, ascorbic acid or a combination thereof) or inorganic reductant (e.g., Fe2 +, Cr2 +, V2 +, Ti3 +, Co2 +, Cu + or a combination thereof) or a combination thereof to produce one or more Radicals In some embodiments, the temperature of the redox reaction is below about 50 ° C, below about 40 ° C, below about 30 ° C, below about 20 ° C, below around 10 ° C or below around 0 ° C. The combination of an oxidative free radical initiator and a reductant is a redox initiator. Free radicals can be generated from the redox initiator to room temperature or at a high temperature.

In some embodiments, the catalyst or initiator is a catalyst or cationic initiator. Some non-limiting examples of suitable cationic initiators include strong protic acids (eg, phosphoric acid, sulfuric acid, hydrofluoric acid, triflic acid or a combination thereof), Lewis acids (eg, SnCl4, AICI3, BF3, and TiCl4). or a combination thereof), stable carbenium ions (trityl cation, tropillium cation or a combination thereof), In some embodiments, the catalyst or initiator is an anionic catalyst or initiator. Some non-limiting examples of suitable anionic initiators include metal amides, metal alkoxides, metal hydroxides, metal cyanides, phosphines, amines and organometallic compounds (Grignard reagents and the organolithium reagents described herein). In certain embodiments, the metal is Cs, K, Na, Li, Mg, Ca or a combination thereof).

The concentration of the catalyst or initiator can be in an amount that can effect the polymerization of farnesene, one or more vinyl monomers or a combination thereof. In some embodiments, the concentration of the catalyst or initiator is at least about 0.01%, about 0.1%, about 0.25%, about 0.5%, about 0.75%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15% or about 20% by weight (or by volume), based on the total weight (or volume) of the composition or emulsion. In certain embodiments, the catalyst or initiator concentration is at most about 0.01%, about 0.1%, about 0.25%, about 0.5%, about 0.75%, about 1%, about 2%, about 3%, around 4%, around 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15% or about 20% by weight ( or in volume), based on the total weight (or volume) of the composition or emulsion.

In some embodiments, the homopolymer of farnesene described herein is prepared by a process comprising the steps of: (a) making a farnesene from a single sugar or a non-fermentable carbon source by the use of a microorganism; Y (b) polymerizing farnesene in the presence of a catalyst described herein.

In certain embodiments, the homopolymer of farnesene described herein is prepared by a process comprising the following steps: (a) making a farnesene of a simple sugar or of a a non-fermentable carbon source through the use of a microorganism; Y (b) copolymerizing the farnesene and at least one vinyl monomer in the presence of a catalyst described herein.

The polymerization step (b) or the copolymerization step (b) of the process described herein can be anionic polymerization, cationic polymerization, free radical polymerization, insertion-catalyzed polymerization and emulsion polymerization.

The anionic polymerization can be carried out in the presence of an anionic catalyst described herein. Anionic polymerization is described in Maurice Morton, "Anionic Polymerization: Principles and Practice". Academic Press, pp 1-244 (1983); and Henry Hsieh et al, "Anionic Polymerization, Principies and Practical Applications". RC Press, pp 1-744 (1996), both of which are incorporated herein by reference.

The cationic polymerization can be carried out in the presence of a cationic catalyst described herein. Cationic polymerization is described in Eric J. Goethals (Editor), "Cationic Polymerization and Related Processes", Academic Press, pp. 1-424 (1984); and Rudolf Faust (Editor), "Cationic Polymerization: Fundamentais and Applications ", American Chemical Society, pp. 1-210 (1997), both of which are incorporated herein by reference.

The free radical polymerization can be carried out in the presence of a free radical initiator described herein. Free radical polymerization is described in G. Moad et al., "The Chemistry of Free Radical Polymerization", Pergamon Press, pp. 1-408 (1996), which are incorporated herein by reference.

In some embodiments, free radical polymerization is carried out by copolymerizing a polymerizable mixture or composition in the presence of at least one free radical initiator to form a farnesene interpolymer, wherein the polymerizable mixture or composition comprises a farnesene and at least one a vinyl monomer, and wherein at least one free radical initiator is hydrogen peroxide, a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxy ester, a peroxy ketone, an azo compound, an organic polyoxide, a photoinitiator, a persulfate or a combination of them. In certain embodiments, farnesene is in an amount greater than 20% by weight, based on the total weight of the polymerizable mixture. In some embodiments, farnesene is -farnesene, ß-farnesene or a combination thereof.

In certain embodiments, at least one vinyl monomer is acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester, vinyl ether, vinyl acetate, acrylonitrile, acrylamide, methacrylamide or a combination thereof. In some embodiments, at least one vinyl monomer is styrene, substituted styrene, a diene of 4-40 carbon atoms, a vinyl halide, vinyl ether, vinyl acetate, vinyl pyridine, vinylidene fluoride, acrylonitrile, acrylic acid, an ester acrylic, methacrylic acid, a methacrylic ester, acrylamide, methacrylamide or a combination thereof. In some embodiments, at least one vinyl monomer comprises a methacrylic ester. In certain embodiments, at least one vinyl monomer comprises styrene. In some embodiments, at least one vinyl monomer comprises butadiene. In certain embodiments, at least one vinyl monomer comprises styrene and butadiene The metal-catalyzed insertion polymerization can be carried out in the presence of a Ziegler-Natta catalyst, Kaminsky catalyst or any other metallocene catalyst described herein.

The emulsion polymerization can be carried out in an emulsion in the presence of a free radical initiator described herein. Emulsion polymerization is described in Chorng-Shyan Chern., "Principies and Applications of Emulsion Polymerization ", John Wiley &Sons Inc., pp. 1-252 (2008), and Peter A. Lovell (Editor)," Emulsion Polymerization and Emulsion Polymers ", John Wiley &Sons Inc., pp. 1-826 (1997), both of which are incorporated herein by reference.

Emulsion polymerization is generally a type of radical polymerization that occurs in an emulsion comprising an emulsion polymerization composition. In some embodiments, the emulsion polymerization composition comprising a) a polymerizable mixture comprising a farnesene and at least one vinyl monomer disclosed herein; b) at least one emulsifier; c) at least one free radical initiator such as those described herein; and d) water.

In some embodiments, the emulsion polymerization is an oil-in-water emulsion, wherein the droplets of monomers (the oil) are emulsified (with emulsifiers) in a continuous phase of water. In certain embodiments, the free radical initiator is soluble in water and the reaction medium is water.

In aqueous emulsion polymerization, water generally forms the continuous medium in which the polymerization takes place. The water may or may not mix with one or more additional solvents that are miscible with water. In some embodiments, the continuous medium comprises water in a quantity of at least about 30% by weight, at least about 40% by weight, at least about 50% by weight, at least about 60% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight or at least about 95% by weight, based on the total weight of the continuous medium.

Some non-limiting examples of suitable emulsifiers include anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and combinations thereof. In some embodiments, one or more anionic surfactants, one or more nonionic surfactants or a combination thereof are used.

Any anionic surfactant that can emulsify an oil in water can be used herein. In some embodiments, the anionic surfactant is or comprises an alkyl sulfate, an alkyl sulfonate, an alkylarylsulfate, an alkylarylsulfonate (for example, alkyl naphthalene sulfonates and alkylbenzene sulfonates), or a combination thereof.

Any nonionic surfactant that can emulsify an oil in water can be used herein. In some embodiments, the nonionic surfactant is or comprises an alkyl polyoxyalkylene, an aryl polyoxyalkylene, a polyoxyalkylene block copolymer, an polyethylene, a polypropylene oxide, a block copolymer of ethylene oxide and propylene oxide or a combination thereof. In other embodiments, the nonionic surfactant is or comprises a polyether polyol, a polyoxyethylene alkyl ether of 8-20 carbon atoms, a polyoxyethylene alkyl aryl ether of 8-20 carbon atoms (eg, polyoxyethylene alkyl phenyl ether of 8-20 carbon atoms), a polyoxyethylene alkyl amine. of 8-20 carbon atoms, a polyoxyethylenealkenylether of 8-20 carbon atoms, a polyoxyethylenealkenylamine of 8-20 carbon atoms, a polyethylene glycol alkyl ether or a combination thereof. Some non-limiting examples of suitable polyoxyethylene alkyl ethers of 8-20 carbon atoms include polyoxyethylene lauryl ether, polyoxyethylene terethylene, polyoxyethylene stearyl ether, branched polyoxyethylene diene ether, polyoxyethylene tridecylether or a combination thereof. Some non-limiting examples of suitable polyoxyethylene alkyl aryl ethers of 8-20 carbon atoms include polyoxyethylenedecylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylenectylphenyl ether or a combination thereof. A non-limiting example of a suitable polyoxyethylene oxide ether of 8-20 carbon atoms is polyoxyethylene oleic ether. Some non-limiting examples of suitable polyoxyethylene alkylamines of 8-20 carbon atoms include polyoxyethylene lauryl amine, polyoxyethylene stearylamine, polyoxyethylene tallow amine or a combination thereof. A non-limiting example polyoxyethylenealkenylamine of 8-20 carbon atoms suitable is polyoxyethylenelethylamine. In other embodiments, the nonionic surfactant is a polyether polyol, polyoxyethylenenonyl phenyl ether, polyoxyethylenddecylphenyl ether, or a combination thereof. In certain embodiments, the nonionic surfactant contains a hydrophilic polyoxyethylene glue.

The emulsion polymerization can occur in a reaction vessel containing an emulsion polymerization composition. In some embodiments, the emulsion polymerization composition comprises a polymerizable mixture comprising a farnesene and at least one vinyl monomer, at least one emulsifier, at least one free ral initiator and water.

The method for the emulsion polymerization of a farnesene with at least one vinyl monomer can be any known method suitable for the emulsion polymerization of olefins and / or vinyl monomers. In some embodiments, the method comprises the copolymerization of farnesene with at least one vinyl monomer in an aqueous medium in the presence of at least one free ral initiator and at least one emulsifier.

Emulsion polymerization of farnesene with minus one vinyl monomer can be used to prepare a polymer emulsion. In some embodiments, the polymer emulsion can be prepared by a method comprising: (a) providing an aqueous emulsion comprising a polymerizable mixture comprising a farnesene and at least one vinyl monomer; at least one emulsifier; at least one initiator; and water; and (b) emulsion polymerization of at least a portion of the polymerizable mixture to form the polymer emulsion. In some embodiments, the method further comprises a step of drying the polymer emulsion to form an emulsion polymer. The polymer emulsion can be dried by any known drying techniques such as direct drying, indirect drying, contact drying, drum drying, vacuum drying, spray drying, dielectric drying, freeze drying, supercritical drying, natural air drying , drying by refractory window, drying by infrared zone or a combination thereof. The dried emulsion polymer can be in any convenient form (eg, powder, granules or film) suitable for handling.

In certain embodiments, farnesene is a-farnesene or β-farnesene or a combination thereof. In some embodiments, farnesene is in an amount of about 10% by weight to about 60% by weight, from about 20% by weight to about 50% by weight, or about 30% by weight to about 40% by weight, based on the total weight of the polymerizable mixture.

Any vinyl monomer disclosed herein may be used for the emulsion polymerization composition. In certain embodiments, at least one vinyl monomer is styrene, substituted styrene, a diene of 4-40 carbon atoms, a vinyl halide, vinyl ether, vinyl acetate, vinyl pyridine, vinylidene fluoride, acrylonitrile, acrylic acid, an ester acrylic, methacrylic acid, a methacrylic ester, acrylamide, methacrylamide or a combination thereof. In some embodiments, at least one vinyl monomer is acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester, vinyl ether, vinyl acetate, acrylonitrile, acrylamide, methacrylamide or a combination thereof. In certain embodiments, at least one vinyl monomer comprises methacrylic acid or acrylic acid and a methacrylic ester. In other embodiments, the methacrylic acid or acrylic acid is present in an amount of from about 0.1% by weight to about 5% by weight, from about 0.25% by weight to about 4% by weight, of about 0.5% by weight. by weight to about 3% by weight, or from about 0.75% by weight to about 2% by weight, based on the total weight of the polymerizable mixture. In other embodiments, methacrylic acid or acrylic acid is present in an amount of about 5% by weight to about 50% by weight, from about 10% by weight to about 40% by weight, from about 15% by weight to about 35% by weight, or about 20% by weight to about 30% by weight, based on the total weight of the polymerizable mixture. In further embodiments, the methacrylic ester is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate or a combination thereof. In some embodiments, at least one vinyl monomer further comprises an acrylic ester. In further embodiments, the methacrylic ester is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate or a combination thereof. In certain embodiments, at least one vinyl monomer comprises acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester, styrene or a combination thereof. In some embodiments, at least one vinyl monomer comprises an acrylic ester, methacrylic acid, a methacrylic ester, styrene or a combination thereof.

The ingredients of the emulsion polymerization composition can be carried together in any way. In some embodiments, two or more of the ingredients of the emulsion polymerization composition, or portions thereof, may be mixed together before the composition of those ingredients or portions thereof is placed in the reaction vessel. In certain embodiments, any ingredients or portions thereof which do not mix together outside the reaction vessel may be added simultaneously or sequentially to the reaction vessel. In other embodiments, any combination of the above methods can be used in providing the ingredients of the emulsion polymerization composition.

After an emulsion polymerization composition is present in the reaction vessel, conditions are provided in which the composition of the emulsion polymerization undergoes emulsion polymerization. In certain embodiments, conditions will be provided as necessary for the free radical initiator to form one or more free radicals. In some embodiments, depending on the free radical initiator used, the reaction mixture may be heated, or a reductant may be added, or the composition of the emulsion polymerization may be exposed to radiation, or a combination thereof. In certain embodiments, other conditions that allow the emulsion polymerization to succeed (such as, for example, monomer emulsification, monomer concentration, concentration of the free radical initiator, etc. are also provided). Such conditions can be found in Chorng-Shyan Chem., "Principles and Applications of Emulsion Polymerization", John Wiley & Sons Inc., pp. 1-252 (2008); and Peter A. Lovell (Editor), "Emulsion Polymerization and Emulsion Polymers", John Wiley & Sons Inc., pp. 1-826 (1997), both of which are incorporated herein by reference.

In some embodiments, the conditions under which the emulsion polymerization composition undergoes emulsion polymerization are established simultaneously with the introduction of the emulsion polymerization composition into the reaction vessel. In other embodiments, the ingredients of the emulsion polymerization composition are not added simultaneously and the conditions under which the emulsion polymerization composition undergoes the emulsion polymerization are established simultaneously with the introduction of the final charge of the polymerization composition. in emulsion in the reaction vessel.

In certain embodiments, the conditions under which the emulsion polymerization composition undergoes the emulsion polymerization are established after the introduction of the emulsion polymerization composition into the reaction vessel. In some embodiments, all the ingredients of the emulsion polymerization composition can be provided in the reaction vessel, and then the emulsion polymerization composition can be heated to a temperature at which at least one portion of at least one free radical initiator constitutes one or more free radicals.

In some embodiments, the conditions under which the emulsion polymerization composition undergoes emulsion polymerization are further established, additional vinyl monomers may be added, additional water may be added, additional emulsifiers may be added, additional initiator free radicals may be added, or A combination of them can be added.

The emulsion polymerization processes can be characterized as single-stage or multi-stage. In one step, a first composition of one or more vinyl monomers is polymerized until the polymerization is complete. If a second composition of one or more vinyl monomers, which may be different from or equal to the first composition, is then polymerized in the presence of the polymer formed in the first stage, the polymerization of the second composition is known as the second stage. . Other subsequent stages can also be performed. In some embodiments, the emulsion polymerization process is a one-step process.

At each stage of an emulsion polymerization process, one or more vinyl monomers are added, either as a shot addition or as a gradual addition or as a combination thereof. In a shot addition, it relatively quickly add one or more vinyl monomers (as compared to the duration of the polymerization time), and then the addition of one or more vinyl monomers is stopped for a time. In a particular step of an emulsion polymerization process involving the addition of shot monomer, a single shot addition can be used to add all of one or more vinyl monomers for that step, or multiple shot additions can be used.

In some embodiments, a free radical inhibitor, such as a nitrous or a nitroxide compound, is introduced into the reaction vessel prior to the start of the polymerization. The presence of such an inhibitor can reduce or eliminate the generation of secondary particles and therefore aids in the care of particle size control of the emulsion polymer. In some embodiments, no free radical inhibitor is introduced into the reaction vessel, such as nitrous or nitroxide compound, prior to the start of the polymerization.

In certain embodiments, one or more vinyl monomers used do not include any vinyl monomer with any acidic group (eg, a carboxylic acid group). In some embodiments, one or more vinyl monomers used do not include any vinyl monomer with any ionic group (for example, an acid group). In some embodiments, the emulsion polymer produced by the process described herein has no ionic group. An ionic group refers to a chemical group that is primarily or completely in ionized form when the emulsion polymer is at a pH ranging from about 2 to about 12.

In some embodiments, at least one of the vinyl monomers used has an acid group or an ionic group. In certain embodiments, the amount of vinyl monomer with an acid group (eg, acrylic acid or methacrylic acid) or ionic group is less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than about 2% by weight, less than about 1.0% by weight, less than about 0.5% by weight, less than about 0.25% by weight, or less than about 0.1% by weight , based on the total weight of the polymerizable mixture. In some embodiments, the amount of the vinyl monomer with an acid group or ionic group is greater than about 50% by weight, greater than about 40% by weight, greater than about 30% by weight, greater than about 20% by weight. % by weight, greater than about 10% by weight, greater than about 5% by weight, or greater than about 1% by weight, based on the total weight of the polymerizable mixture. In certain embodiments, the amount of vinyl monomer with an acidic group or ionic group is from about 0.1% by weight to about 60% by weight, from about 1% by weight to about 50% by weight, from about 5% by weight to about 45% by weight. weight, from about 10% by weight to about 40% by weight, from about 15% by weight to about 35% by weight, from about 0.1% by weight to about 20% by weight, from about 0.1% by weight, to about 10% by weight, or from about 0.1% by weight to about 5% by weight, based on the total weight of the polymerizable mixture.

The concentration of the emulsifier can be in any amount that can effectively emulsify the polymerizable mixture in water. In some embodiments, the concentration of the emulsifier is at least about 0.01%, about 0.1%, about 0.25%, about 0.5%, about 0.75%, about 1%, about 2%, about 3% , about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15% or about 20% by weight (or about volume), based on the total weight (or volume) of the emulsion polymerization composition. In certain embodiments, the concentration of the surfactant is greater than about 0.01%, about 0.1%, about 0.25%, about 0.5%, about 0.75%, about 1%, about 2%, about 3 %, around 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15% or about 20% by weight (or volume), based on the total weight (or volume) of the emulsion polymerization composition.

In some embodiments, the Mw of the emulsion polymers described herein is greater than about 5,000, greater than about 10,000, greater than about 50,000, greater than about 100,000, greater than about 200,000, greater than about 500,000, greater than about 1,000,000, greater than about 1,000,000, greater than about 1,000,000, greater than about 2,000,000, greater than about 3,000,000 or greater than about 4,000,000.

In certain embodiments, the emulsion polymers described herein have at least a glass transition temperature (Tg) of about -70 ° C to about 40 ° C, of about -60 ° C to about 30 °. C or around -50 to around 20 ° C, measured according to AST D7426-08 standard. In some embodiments, the Tg is from about -60 ° C to about 0 ° C, from about -50 ° C to about 0 ° C, from about -40 ° C to about 0 ° C, about -30 ° C to about 0 ° C, about -60 ° C to about 10 ° C or about -50 ° C to about 20 ° C. In certain modalities, the Tg is around -30 ° C at about 30 ° C, about -20 ° C to about 30 ° C, about -10 ° C to about 20 ° C, about -5 ° C to about 25 ° C, around 0 ° C to around 20 ° C, or around 5 ° C to around 15 ° C.

In certain embodiments, the emulsion polymer described herein is in the form of polymer particles dispersed in a continuous aqueous medium to form a polymer emulsion. In some embodiments, the polymer particles have an average diameter greater than about 10 nm, greater than about 20 nm, greater than about 25 nm, greater than about 50 nm, greater than about 75 nm, or greater than about around 100 nm. In some embodiments, the polymer particles have an average diameter of less than about 2,000 nm, less than about 1,000, less than about 500 nm, less than about 250 nm, or less than about 100 nm.

In some embodiments, the polyfarnesene described herein is prepared by the polymerization of a β-farnesene in the presence of a catalyst, where the amount of the cis-1,4-microstructure in the polyfarnesene is greater than about 80% by weight , greater than about 75% by weight, greater than about 70% by weight, greater than about 65% by weight, or greater than about 60% by weight, based on the total weight of polyfarnesene. In some embodiments, β-farnesene is copolymerized with a vinyl monomer for form a farnesine copolymer. In other embodiments, the vinyl monomer is styrene. In other embodiments, the farnesene copolymer is a block copolymer.

In certain embodiments, the polyfarnesene described herein is prepared by polymerizing an α-farnesene in the presence of a catalyst, wherein the amount of the cis-1,4-microstructure in the polyfarnesene is about 1% by weight at about 99% by weight, from about 10% by weight to about 99% by weight, from about 20% by weight to about 99% by weight, from about 30% by weight to about 99% by weight weight, from about 40% by weight to about 99% by weight, from about 50% by weight to about 99% by weight, from about 1% by weight to about 99% by weight, from about 1% by weight to about 90% by weight, from about 1% by weight to about 80% by weight, from about 1% by weight to about 70% by weight, or about 1% by weight to about 60% by weight, based on the total weight of polyfarnesene. In some embodiments, α-farnesene is copolymerized with a vinyl monomer to form a farnesin copolymer. In other embodiments, the vinyl monomer is styrene. In other embodiments, the farnesene copolymer is a block copolymer.

In some embodiments, the polyfarnesene described herein may be partially or completely hydrogenated by a hydrogenation agent also known to an experienced person. For example, a saturated polyfarnesene can be prepared by (a) polymerizing a farnesene described herein in the presence of a catalyst described herein to form a polyfarnesene; and (b) hydrogenating at least a portion of the double bonds in the polyfarnesene in the presence of a hydrogenation reagent. In some embodiments, farnesene is copolymerized with a vinyl monomer described herein to form a farnesene copolymer. In other embodiments, the vinyl monomer is styrene. In other embodiments, the farnesene copolymer is a block copolymer. In still other embodiments, farnesene is an α-farnesene or a β-farnesene or a combination thereof.

In certain embodiments, the hydrogenation reagent is hydrogen in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd / C, Pt, Pt02, Ru (PPh3) 2Cl2, Raney nickel or a combination thereof. In one embodiment, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In another embodiment, the catalyst is 10% Pd / C in a high pressure reaction vessel and the hydrogenation reaction is allowed to proceed to completion. Generally, after it is completed, the reaction mixture can be washed, concentrated and dried to produce the corresponding hydrogenated product. Alternatively, any reducing agent that can reduce a C = C bond to a C-C bond can also be used. For example, polyfarnesene can be hydrogenated by treatment with hydrazine in the presence of a catalyst, such as 5-ethyl-3-methyl-lumiflavine perchlorate, under an oxygen atmosphere to give the corresponding hydrogenated products. The reduction reaction with hydrazine is described in Imada et al., J. Am. Chem. Soc, 127, 14544-14545 (2005), which is incorporated herein by reference.

In some embodiments, at least a portion of the C = C bonds of the polyfarnesene described herein are reduced to the corresponding C-C bonds by hydrogenation in the presence of a catalyst and of hydrogen at room temperature. In other embodiments, at least a portion of the C = C bonds of one or more of the formulas (I ') ~ (III'), (V ') - (VII'), and (XI) - (XIV) and the stereoisomers thereof are reduced to the corresponding CC bonds by hydrogenation in the presence of a catalyst and of hydrogen at room temperature. In other embodiments, the hydrogenation catalyst is 10% Pd / C.

In certain embodiments, the vinyl monomer is styrene. In some embodiments, farnesene is a -farnesene or a β-farnesene or a combination thereof. In other modalities, farnesene is prepared by means of use of a microorganism. In other embodiments, farnesene is derived from a simple sugar or from a non-fermentable carbon source.

Farnesene Farnesene, such as α-farnesene and β-farnesene, can be derived from any source or prepared by any method known to a person skilled in the art. Some known methods are described in U.S. Patent No. 7,655,739, which is incorporated herein by reference. In some embodiments, farnesene is derived from a chemical source (eg, petroleum or coal) or obtained by a synthetic chemical method. In other embodiments, farnesene is prepared by fractional distillation of petroleum or coal tar. In other embodiments, farnesene is prepared by any known chemical synthetic method. One of the examples that is not limited to an appropriate synthetic chemical method, includes the dehydration of nerolidol with phoryl chloride in pyridine as described in the article written by Anet EFLJ, "Synthesis of (E, Z) -a -, ( Z, Z) -a-, and (Z) -β-farnesene ", Aust. J. Chem., 23 (10), 2101-2108 (1970), which is incorporated herein by reference.

General Procedures for Making Polyphames The polymerization of a farnesene or the copolymerization of a farnesene with one or more vinyl comonomers and / or one or more functional comonomers can be carried out over a wide temperature range. In certain embodiments, the polymerization temperature is from about -30 ° C to about 280 ° C, from about 30 ° C to about 180 ° C, or from about 60 ° C to about 100 ° C. The partial pressures of the vinyl monomers may be within a range of about 0.1 MPa (15 psig) to about 245 MPa (50,000 psig), from about 0.1 MPa (15 psig) to about 172.5 MPa (25,000) psig), from around 0.1 MPa (15 psig) to around 69 MPa (10,000 psig), from around 0.1 MPa (15 psig) to around 34.5 MPa (5,000 psig) or around 0.1 MPa (15 psig) at around 6.9 MPa (1,000 psig).

The concentration of the catalyst used to make the polifarriesenos described herein depends on many factors. In some embodiments, the concentration ranges from about 0.01 micromoles per liter to about 100 micromoles per liter. The polymerization time depends on the type of process, the concentration of the catalyst and other factors. Generally, the polymerization time is within several minutes to several hours.

A non-limiting example of the free radical polymerization process for the interpolymer of Farnesene is described below. A farnesene such as β-farnesene and one or more vinyl monomers described herein and / or one or more functional comonomers described herein may be added to a solvent such as cyclohexane to form a polymerizable mixture in a reactor, optionally under a nitrogen or argon atmore. The polymerizable mixture can be dried over a drying agent such as molecular sieves. The polymerizable mixture is polymerized by a free radical catalyst described herein at room temperature or at an elevated temperature until all or a substantial portion of monomers is consumed.

A non-limiting example of the emulsion polymerization process for the farnesene interpolymer is described below. A farnesene such as β-farnesene, one or more vinyl monomers described herein and / or one or more functional comonomers described herein and a surfactant described herein may be added to the water, in a reactor optionally under an atmore of nitrogen or argon. The mixture is stirred to form an emulsion mixture. The emulsion mixture is polymerized by a free radical catalyst described herein at room temperature or at an elevated temperature until all or a substantial portion of monomers is consumed.

Polyfarnesene Compositions The polypharmames can be used to prepare polyfarnesene compositions for a wide variety of applications. In some embodiments, the polyfarnesene compositions comprise the polyfarnesene described herein and a second polymer or at least one additive. In certain embodiments, the polyfarnesene compositions comprise a second polymer. In other embodiments, the polyfarnesene compositions do not comprise a second polymer. The second polymer can be a vinyl or polyfarnesene polymer, a non-vinyl or polyfarnesene polymer, or a combination thereof. Some non-limiting examples of vinyl polymers and polyphatnes are described in Malcolm P. Stevens, "Polymer Chemistry, an Introduction" Third Edition, Oxford University Press, pp. 17-21 and 167-279 (1999), which is incorporated herein by reference. Some non-limiting examples of the second suitable polymer include a polyolefin, polyurethane, polyester, polyamide, styrenic polymer, phenolic resin, polyacrylate, polymethacrylate or a combination thereof.

In certain embodiments, the ratio of polyfarnesene to the second polymer is from about 1:99 to about 99: 1, from about 1:50 to about 50: 1, from about 1:25 to about 25: 1. or around 1:10 to around 10: 1.

In some embodiments, the second polymer is a polyolefin (eg, polyethylene, polypropylene, an ethylene / α-olefin interpolymer, a copolymer of ethylene and propylene, and a copolymer of ethylene and vinyl acetate (EVA)), polyurethane, polyester, polyamide, styrenic polymer (for example, polystyrene, poly (acrylonitrile-butadiene-styrene), poly (styrene-butadiene-styrene) and the like), phenolic resin, polyacrylate, polymethacrylate or a combination thereof. In some embodiments, the second polymer is polyethylene, polypropylene, polystyrene, a copolymer of ethylene and vinyl acetate, poly (acrylonitrile-butadiene-styrene), poly (styrene-butadiene-styrene) or a combination thereof. The second polymer can be combined with the farnesin interpolymer before it is added to the polyfarnesene composition. In some embodiments, the second polymer is added directly to the polyfarnesene composition without pre-combining with the farnesin interpolymer.

The weight ratio of polyfarnesene to the second polymer in the polymer composition can be between about 1:99 and about 99: 1, between about 1:50 and about 50: 1, between about 1:25 and about of 25: 1, between about 1:10 and about 10: 1, between about 1: 9 and about 9: 1, between about 1: 8 and around 8: 1, between about 1: 7 and about 7: 1, between about 1: 6 and about 6: 1, between about 1: 5 and about 5: 1, between about 1: 4 and around 4: 1, between about 1: 3 and about 3: 1, between about 1: 2 and about 2: 1, between about 3: 7 and about 7: 3 or between about 2: 3 and around 3: 2.

In some embodiments, the second polymer is a polyolefin. Any polyolefin that is partially or totally compatible with polyfarnesene can be used. Non-limiting examples of suitable polyolefins include polyethylenes; polypropylenes; polybutylenes (for example, polybutene-1); polypenten-1; polyhexen-1; poliocten-1; polidecen-1; poly-3-methylbuten-1; poly-4-methylpenten-1; polyisoprene; polybutadiene; poly-1,5-hexadiene; olefin-derived interpolymers; interpolymers derived from olefins and other polymers such as polyvinyl chloride, polystyrene, polyurethane, and the like; and mixtures thereof. In some embodiments, the polyolefin is a homopolymer such as polyethylene, polypropylene, polybutylene, polypenten-1, poly-3-methylbuten-1, poly-4-methylpenten-1, polyisoprene, polybutadiene, poly-1,5-hexadiene, polyhexen -1, poliocten-1 and polyidecen-1.

Some non-limiting examples of suitable polyethylenes include ultra low density polyethylene (ULDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high molecular weight high density polyethylene (HMW-HDPE), ultra high molecular weight polyethylene (UHMW-PE) and combinations thereof. Some non-limiting examples of polypropylenes include low density polypropylene (LDPP), high density polypropylene (HDPP), high melt strength polypropylene (HMS-PP) and combinations thereof. In some embodiments, the second polymer is or comprises polypropylene of high melt strength (HMS-PP), low density polyethylene (LDPE) or a combination thereof.

In some embodiments, the polyfarnesene compositions described herein comprise at least one additive for the purposes of improving and / or controlling the processability, appearance, physical, chemical and / or mechanical properties of the polyfarnesene compositions. In some embodiments, the polyfarnesene compositions do not comprise an additive. Any additive plastics known to a person skilled in the art can be used in the polyfarnesene compositions described herein. Non-limiting examples of suitable additives include fillers, graft initiators, thickeners, glidants, anti-blocking agents, plasticizers, antioxidants, agents blowing agents, blowing agent activators (for example, zinc oxide, zinc stearate and the like), UV stabilizers, acid scavengers, dyes or pigments, co-agents (for example, triallyl cyanurate), lubricants, anti-aging agents -condensation, flow aids, processing aids, extrusion aids, coupling agents, crosslinking agents, stability control agents, nucleating agents, surfactants, solvents, pyro-retardants, antistatic agents, and combinations thereof. Some suitable additives for making the polyfarnesene composition are described in U.S. Patent No. 7,655,739, which is incorporated herein by reference.

The total amount of the additives can range from about more than 0 to about 80%, from about 0.001% to about 70%, from about 0.01% to about 60%, of about 0.1% around 50%, from about 1% to about 40%, or from about 10% to about 50% of the total weight of the polymer composition. Some additive polymers have been described in Zweifel Hans et al., "Plastics Additives Handbook" Hanser Gardner Publications, Cincinnati, Ohio, 5th edition (2001), which is incorporated herein by reference in its entirety.

Optionally, the polyfarnesene compositions described herein may comprise a plasticizer.

In general, a plasticizer is a chemical that can increase flexibility and decrease the glass transition temperature of polymers. Any plasticizer known to a person skilled in the art can be added to the polyfarnesene compositions described herein. Non-limiting examples of plasticizers include mineral oils, abietates, adipates, alkylsulfonates, azelates, benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils, isobutyrates, oleates, pentaerythritol derivatives, phosphates, phthalates, esters , polybutenes, ricinoleates, sebacates, sulfonamides, tri- and pyromelitates, biphenyl derivatives, stearates, difuran diesters, fluoride-containing plasticizers, hydroxybenzoic esters, isocyanate adducts, multiple ring aromatics, natural products derivatives, nitriles, plasticizers based on siloxane, tar-based products, thioethers and combinations thereof. Where used, the amount of the plasticizer in the polymer composition can be from more than 0 to about 15% by weight, from about 0.5 to about 10% by weight, or from about 1 to about 5% by weight. weight of the total weight of the polymer composition. Some plasticizers have been described in George Wypych, "Handbook of Plasticizers", ChemTec Publishing, Toronto-Scarborough, Ontario (2004), which are incorporated herein by reference.

In some embodiments, the polyfarnesene compositions described herein optionally comprise an antioxidant that can prevent the oxidation of polymer compounds and organic additives in the polyfarnesene compositions. Any antioxidant known to a person skilled in the art can be added to the polyfarnesene compositions described herein. Nonlimiting examples of suitable antioxidants include aromatic amines such as alquildifenilaminas or inhibited, phenyl-a-naphthylamine, alkyl- or aralquilfenil--naphthylamine substituted, alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamine and the like; phenols such as 2,6-di-t-butyl-4-methylphenol; 1, 3, 5-trimethyl-2,4,6,6-tris (3 ', 5'-di-t-butyl-4' -hydroxybenzyl) -benzene; tetrakis [(methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane (for example, IRGANOX ™ 1010, from Ciba Geigy, New York); acryloyl-modified phenols; octadecyl-3,5-dihydroxy t-butyl-4-hydroxycinnamate (e.g., IRGANOX ™ 1076, commercially available from Ciba Geigy); phosphites and phosphonites; hydroxylamines; benzofuranone derivatives;. and combinations thereof Where used, the amount of antioxidant in the composition polymer can be around more than 0 to about 5% by weight, from about 0.0001 to about 2.5% in weight, from about 0.001 to about 1% by weight, or from about 0.001 to about 0.5% by weight of the total weight of the polymer composition. Some antioxidants have been described in Zweifel Hans et al., "Plastics ñdditives Handbook", Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 1, pages 1-140 (2001), which are incorporated herein by reference.

In other embodiments, the polyfarnesene compositions described herein optionally comprise a UV stabilizer that can prevent or reduce the degradation of polyfarnesene compositions by UV radiation. Any UV stabilizer known to a person skilled in the art can be added to the polyfarnesene compositions described herein. Nonlimiting examples of UV stabilizers suitable include benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidines, carbon black, hindered amines, extinguishers nickel, hindered amines, phenolic antioxidants, metallic salts, zinc compounds and combinations thereof . Where used, the amount of the UV stabilizer in the polymer composition can be from about more than 0 to about 5% by weight, from about 0.01 to about 3% by weight, from about 0.1 to about 2% by weight, or from about 0.1 to about 1% by weight of the total weight of the composition of polymer. Some UV stabilizers have been described in Zweifel Hans et al, "Plastics Additives Handbook" by Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 2, pages 141-426 (2001), which are incorporated herein by reference.

In other embodiments, the polyfarnesene compositions described herein optionally comprise a colorant or pigment that can change the appearance of the polyfarnesene compositions to the eyes of the human. Any colorant or pigment known to a person skilled in the art can be added to the polyfarnesene compositions described herein. Nonlimiting examples of colorants or suitable pigments include inorganic pigments such as metal oxides such as iron oxide, zinc oxide, and titanium dioxide, mixed metal oxides, carbon black, organic pigments such as anthraquinones, anthanthrones, azo compounds and monoazo, arylamides, benzimidazolones, lacquers BONA, dicetopirrol-pyrroles, dioxazines, disazo compounds, diarylide compounds, flavanthrones, indanthrones, isoindolinones, isoindolines, metal complexes, salts monoazo, naphthols, b-naphthols, naphthol AS, lacquers naphthol, perylenes , perinones, phthalocyanines, pyrantrones, quinacridones, and quinophthalones, and combinations thereof. Where it is used, the amount of the colorant or The pigment in the polymer composition can be from about 0 to about 10% by weight, from about 0.1 to about 5% by weight, or from about 0.25 to about 2% by weight of the total weight of the polymer. the polymer composition. Some dyes have been described in Zweifel Hans et al., "Plastics Additives Handbook", Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 15, pages 813-882 (2001), which are incorporated herein by reference.

Optionally, the polyfarnesene compositions described herein may comprise a filler, which may be used to adjust, inter alia, volume, weight, costs, and / or technical performance. Any filler known to a person skilled in the art can be added to the polyfarnesene compositions described herein. Nonlimiting examples of suitable fillers include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina such as alumina trihydrate, glass microsphere, microsphere ceramic, thermoplastic microsphere, barite, wood flour, glass fibers, carbon fibers, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, oxide zinc, barium sulfate, dioxide titanium, titanates and combinations thereof. In some embodiments, the filler is barium sulfate, talcum, calcium carbonate, silica, glass, fiberglass, alumina, titanium dioxide, or a mixture thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, fiberglass or a mixture thereof. Where used, the amount of the filler in the polymer composition can be about greater than 0 to about 80% by weight, from about 0.1 to about 60% by weight, from about 0.5 to about 40% by weight, from about 1 to about 30% by weight, or from about 10 to about 40% by weight of the total weight of the polymer composition. Some fillers have been described in U.S. Patent No. 6,103,803 and Zweifel Hans et al, "Plastics Additives Handbook" Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 17, pages 901-948 (2001), both of which are incorporated herein by reference.

In some embodiments, the polyfarnesene compositions described herein comprise a thickening agent. In other embodiments, the polyfarnesene compositions described herein do not comprise a thickening agent. Any material that can be added to an elastomer to produce an adhesive can be used herein as a thickening agent. Some non-limiting examples of thickeners include a natural resin and modified a glycerol or pentaerythritol ester of natural or modified resin; a copolymer or terpolymer of natural terpene; a polyterpene resin or a hydrogenated polyterpene resin; a phenolic modified terpene resin or a hydrogenated derivative thereof; an aliphatic or cycloaliphatic hydrocarbon resin or a hydrogenated derivative thereof; an aromatic hydrocarbon resin or a hydrogenated derivative thereof; an aliphatic or aromatic modified cycloaliphatic hydrocarbon resin or a hydrogenated derivative thereof; or a combination thereof. In certain embodiments, the thickening agent has a ring and ball softening point (R &B) equal to or greater than 60 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C or 100 ° C, as measured in accordance with ASTM 28-67, which is incorporated herein by reference. In certain embodiments, the thickening agent has a softening point of R &B equal to or greater than 80 ° C, as measured in accordance with ASTM 28-67.

In certain embodiments, the amount of thickening agent in the polyfarnesene compositions described herein is in the range of about 0.1 wt% to about 70 wt%, from about 0.1 wt% to about 60 wt% weight, from about 1% by weight to about 50% by weight, or from about 0.1% by weight to about 40% by weight or about 0.1% by weight about 30% by weight or from about 0.1% by weight to about 20% by weight, or from about 0.1% by weight to about 10% by weight, based on the total weight of the composition. In other embodiments, the amount of thickening agent in the composition described herein is in the range of about 1% by weight to about 70% by weight, from about 5% by weight to about 70% by weight, from about 10% by weight to about 70% by weight, from about 15% by weight to about 70% by weight, from about 20% by weight to about 70% by weight, or about 25% by weight % by weight to about 70% by weight, based on the total weight of the composition.

Optionally, the polyfarnesene compositions described herein may be partially or completely crosslinked. When crosslinking is desired, the polyfarnesene compositions described herein comprise a crosslinking agent which can be used to carry out the crosslinking of the polyfarnesene compositions, thereby increasing their moduli and inflexibility, among other things. An advantage of a polyfarnesene composition is that crosslinking can occur in its secondary chains in place of the base column polymer like other polymers such as polyisoprene and polybutadiene. Any crosslinking agent known to a person skilled in the art can be added to the polyfarnesene compositions described herein. Non-limiting examples of suitable crosslinking agents include organic peroxides (eg, alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacylperoxides, peroxyketals, and cyclic peroxides) and silanes (eg, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) ) silane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, and 3-methacryloyloxypropyltrimethoxysilane). Where used, the amount of the crosslinking agent in the polymer composition can be from about more than 0 to about 20% by weight, from about 0.1% by weight to about 15% by weight, or from about 1% by weight to about 10% by weight of the total weight of the polymer composition. Some suitable crosslinking agents have been described in Zweifel Hans et al, "Plastics Additives Handbook" by Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 14, pages 725-812 (2001), both of which are incorporated herein. for reference.

In some embodiments, the farnesin interpolymer described herein includes farnesene-modified polymers prepared by copolymerization of one or more farnesene with one or more vinyl monomers. In certain embodiments, the unmodified polymer derivatives of one or more vinyl monomers may be any homopolymer or known olefin interpolymer. In other embodiments, none of one or more other vinyl monomers has an unsaturated side chain capable of reacting with a crosslinking agent. Due to the derivatives of unsaturated side chains of farnesene, the farnesene modified polymer described herein can be crosslinked by a crosslinking agent described herein.

In certain embodiments, the amount of farnesene in the farnesene-modified polymer described herein is from about 1% by weight to about 20% by weight, from about 1% by weight to about 10% by weight, about 1% by weight to about 7.5% by weight, from about 1% by weight to about 5% by weight, from about 1% by weight to about 4% by weight, of about 1% by weight weight to about 3% by weight, or from about 1% by weight to about 2% by weight, based on the total weight of the modified farnesin polymer. In other embodiments, the amount of one or more other vinyl monomers in the modified farnesene polymer described herein is from about 80 wt% to about 99 wt%, of about 90 wt% to about of 99% by weight, from about 92.5% by weight to about 99% by weight, from about 95% by weight to about 99% by weight, from about 96% by weight to about 99% by weight , from about 97% by weight to about 99% by weight, or about 98% by weight to about 99% by weight, based on the total weight of the modified farnesin polymer.

Mixture of the Ingredients of the Polymer Compositions The ingredients of the polyfarnesene compositions, ie, the farnesene interpolymer, the additive, the second optional polymer (eg, polyethylene, and polypropylene) and additives (eg, the crosslinking agent) can be mixed or blended using known methods by a person with experience in the technique. Non-limiting examples of suitable combination methods include melt blending, solvent blending, extrusion, and the like.

In some embodiments, the ingredients of the polyfarnesene compositions are combined by dissolving by a method as described by Guerin et al., In U.S. Patent No. 4,152,189. First, all solvents, if any, are removed from the ingredients by heating at an appropriate elevated temperature of about 100 ° C to about 200 ° C or about 150 ° C to about 175 ° C at a pressure of about from 5 torr (667 Pa) to around 10 torr (1333 Pa). Next, the ingredients are weighed into a container in the desired proportions and the foam is formed by heating the contents of the container to a liquid state while stirring.

In other embodiments, the ingredients of the articles are processed using a solvent combination. First, the desired foam ingredients are dissolved in a suitable solvent and the mixture is then mixed or blended. Next, the solvent is removed to provide the foam.

In the additional embodiments, the physical combination devices can provide dispersive mixture, distributive mixture, or a combination of dispersive and distributive mixture that can be used to prepare homogeneous combinations. Both the batch and the continuous methods of the physical combination can be used. Non-limiting examples of batch methods include those methods using BRABENDER® mixing equipment (for example, BRABENDER PREP CENTER®, available from CW Brabender Instruments, Inc., South Hackensack, NJ) or BANBURY® internal mixing and roll-shredding equipment (available from Farrel Company, Ansonia, Conn.). Non-limiting examples of continuous methods include single screw extrusion, twin screw extrusion, disk extrusion, single screw oscillating extrusion, and single bolt screw bolt extrusion. In some embodiments, the additives may be added in an extruder through a feed hopper or feed throat during the extrusion of the farnesene interpolymer, the second polymer optional or foam. The mixture or combination of polymers by extrusion has been described in C. Rauwendaal, "Polymer Extrusion", Hanser Publishers, New York, NY, pages 322-334 (1986), which is incorporated herein by reference.

When one or more additives are required in the polyfarnesene compositions, the desired amounts of the additives may be added in one charge or multiple charges to the farnesene interpolymer, the second polymer or the polymer composition. In addition, the addition can take place in any order. In some embodiments, the additives are first added and mixed or combined with the farnesin interpolymer and then the interpolymer-containing additive is combined with the second polymer. In other embodiments, the additives are first added and mixed or combined with the second polymer and then the additive containing the second polymer is combined with the farnesin interpolymer. In other embodiments, the farnesene interpolymer is first combined with the second polymer and then the additives are combined with the polymer composition.

The ingredients of the polymer composition can be blended or combined in any suitable mixing or combination devices known to the skilled person. The ingredients in the polymer composition can then be mixed at a temperature below the decomposition temperature of the blowing agent and the crosslinking agent to ensure that all ingredients are mixed homogeneously and remain intact. After the polymer composition is mixed relatively homogeneously, the composition is formed and then exposed to conditions (e.g., heat, pressure, shear, etc.) for a period of time sufficient to activate the blowing agent and the crosslinking agent to make the foam.

Applications of the Compositions that comprise the Polifámesenos The polypharmames or polyfarnesene compositions described herein, can be used for a wide variety of applications. For example, they can be used in a variety of conventional thermoplastic manufacturing processes to produce useful articles, which include objects comprising at least one film layer, such as a monolayer film, or at least one layer in a film of multilayer prepared by melting, blowing, calendering process, or extrusion coating; molded articles, such as blow molding, injection molding, or rotomolded articles; extrusions; fibers; and woven or non-woven fabrics. The thermoplastic compositions comprise the present polymer, including combinations with other polymers, natural or synthetic additives, agents reinforced, ignition resistant additives, antioxidants, stabilizers, colorants, extenders, crosslinkers, blowing agents, and plasticizers. Of particular utility are multi-component fibers of fibers such as core / sheath fibers, having an outer surface layer, comprising at least in part, one or more polymers of the invention.

The fibers that can be prepared from the polypharmames or polyfarnesene compositions described herein include staple fibers, tow, multicomponent, sheath / core, braid, and monofilament. Any fiber formation processes can be used in the present. For example, suitable fiber forming processes include continuous filament, meltblown, gel spinning, woven and nonwoven fabrics, or structures made of such fibers, including combinations with other fibers, such as polyester, nylon or cotton, thermoformed articles, extruded shapes, including profile extrusions and co-extrusions, calendered, and twisted, braided, or crimped yarns or fibers. The polypharmames or polyfarnesene compositions described herein are also useful for wire and cable coating operations, as well as in sheet extrusion for vacuum forming operations, and forming molded articles, which include the use of coating processes. injection molding, blow molding, or rotomolding processes. The polypharmames or polyfarnesene compositions described herein may also be formed into manufactured articles such as those previously mentioned using conventional polyolefin process techniques that are well known to those skilled in the polyolefin process art.

Dispersions or emulsions (both aqueous and non-aqueous) can also be formed using the polypharmames or the polyfarnesene compositions described herein. The foams comprising the polypharmames or polyfarnesene compositions described herein may also be formed. The polymers can also be crosslinked by any known means, such as the use of peroxide, electron beam, silane, azide, or other crosslinking techniques. The polymers can also be chemically modified, such as by grafting (for example by the use of maleic anhydride (MAH), silanes, or other grafting agent), halogenation, amination, sulfonation, or other chemical modification.

Suitable end uses for the foreign products include films and elastic fibers; soft touch products, such as toothbrush handles and appliance handles; packaging and profiles; adhesives (including heat-melting adhesives and sensitive adhesives to pressure); footwear (including shoe soles and shoe linings); interior parts and profiles of car; foam products (both open and closed cell); impact modifiers for other thermoplastic polymers such as high density polyethylene, isotactic polypropylene, or other olefin polymers; coated fabrics; hoses; pipeline; weather stripping; cover linings; floor covering; and viscosity index modifiers, also known as pour point modifiers, for lubricants.

The polyfarnesene compositions described herein may also be used to make articles for various applications such as automotive, construction, medical, food and beverage, electrical, household appliances, commercial machines, and markets. In some embodiments, the polyfarnesene compositions are used to make molded parts or selected items of toys, handles, soft touch handles, friction stop bands, floor coverings, car mats, wheels, swivel wheels, furniture legs and appliances, labels, seals, packaging such as static and dynamic packaging, automotive doors, bumper fascia, grill components, stirrups, hoses, linings, office equipment, linings, diaphragms, pipes, caps, plugs, plunger tips, systems of supply, earthenware kitchen, shoes, shoe cameras and shoe soles.

The polymeric emulsions described herein can be used for various applications such as paints, coatings, such as paper coatings and textile coatings, adhesives and rheology modifiers.

In some embodiments, the polyfarnesene compositions described herein are used to prepare molded articles, films, sheets and foams with known polymer processes such as extrusion (e.g., sheet extrusion and profile extrusion); molding (e.g., injection molding, rotational molding, and blow molding); fiber spinning; and film blowing and casting film processes. In general, extrusion is a process by which a polymer is continuously propelled together with a screw through regions of high temperature and pressure where it melts and compacts, and finally it is forced through the die. The extruder can be a single screw extruder, a multiple screw extruder, a disk extruder or a piston extruder. The die can be a film die, blow film die, sheet die, pipe die, pipe die or profile extrusion die. The extrusion of polymers has been described in C. Rauwendaal, "Polymer Extrusion", Hanser Publishers, New York, NY (1986); and MJ.

Stevens, "Extruder Principis and Operation", Ellsevier Applied Science Publishers, New York, NY (1985), both of which are incorporated herein by reference in their entirety.

Injection molding is also widely used to make a variety of plastic parts for various applications. In general, injection molding is a process by which a polymer is melted and injected under high pressure into a mold, which is the inverse of the desired shape, to form parts of the desired shape and size. The mold can be made of metal, such as steel and aluminum. Polymer injection molding has been described in Beaumont et al., "Successful Injection Molding: Process, Design, and Simulation", Hanser Gardner Publications, Cincinnati, Ohio (2002), which is incorporated herein by reference in its entirety. .

Molding is generally a process by which a polymer melts and conducts in a mold, which is the inverse of the desired shape, to form parts of the desired shape and size. The molding can be without pressure or pressure assisted. Polymer molding is described in Hans-Georg Elias "An Introduction to Plastics", Wiley-VCH, einhei, Germany, p. 161-165 (2003), which is incorporated herein by reference.

Rotational molding is a generally Used to produce hollow plastic products. Using additional post-molding operations, complex compounds that can be effectively produced as other molding and extrusion techniques. All the different rotational torques of other processing methods where the stages of heat, fusion, molding, and cooling occur after the polymer that is placed in the mold, so that no external pressure is applied during the formation. Polymer rotational molding has been described in Glenn Beall, "Rotational Molding: Design, Materials &Processing", Hanser Gardner Publications, Cincinnati, Ohio (1998), which is incorporated herein by reference in its entirety.

Blow molding can be used to make hollow plastic containers. The process involves placing a softened polymer in the center of a mold, inflating the polymer against the walls of the mold with a blow pin, and solidifying the product by cooling. There are three general types of blow molding: extrusion blow molding, injection blow molding, and blow molding by expansion, injection blow molding can be used to process polymers that can not be extruded. The blow molding by expansion can be used to hinder the blowing of crystalline and crystallized polymers such as polypropylene. The blow molding of polymers has been described in Norman C.

Lee, "Understanding Blow Molding" Hanser Gardner Publications, Cincinnati, Ohio (2000), which is incorporated herein by reference in its entirety.

The following examples are present to exemplify the embodiments of the invention but it is not intended to limit the invention to the specific modalities established. Unless otherwise indicated, all parts and percentages are by weight. All numerical values are approximate. When the numerical limits are given, it should be understood that the modalities outside the established limits may still fall within the scope of the invention. The specific details described in each example should not be construed as necessary features of the invention.

EXAMPLES Purification of Starting Materials The β-farnesene which is 97.6% pure by weight is obtained from Amyris Inc., Emeryville, CA. β-farnesene including hydrocarbon-based impurities such as zingiberene, bisabolene, farnesene epoxide, farnesol isomer, E, E-farnesol, squalene, ergosterol, and some farnesene dimers. The β-farnesene is purified with a 3Á molecular sieve to remove the impurities and then distilled again under a nitrogen atmosphere to improve the purity. The cyclohexane that is distilled under a nitrogen atmosphere removes moisture and is stored with a drying agent.

Differential Scan Calorimetry A TA Q200 differential scanning calorimeter is used to determine glass transition temperatures (Tg) of the polymer samples described herein. A sample of 5 mg is placed in an aluminum mold. An empty reference molding and sample mold is maintained within ± 0.01 mg. Samples are examined at about -175 ° C to about 75 ° C at a rate of 10 ° C / min. Tg is identified as a stage of transition change in the thermal flux. The midpoint of transition is reported as the Tg of the sample.

Gel Permeation Chromatography The GPC is used to determine the molecular weights and polydispersities of polymer samples. A Waters 2414 refractive index detector is used with a Waters 1515 isocratic HPLC pump. HPLC grade tetrahydrofuran is used as the solvent. The polydispersed fractions are collected from GPC. The molecular weight of a sample is generally recorded as the number of molecular weight averaged (Mn) or the weight average (Mw). When the peaks that forbade the determination of a single polydispersity of each peak are overlapped, a peak molecular weight (Mp) is incorporated herein.

Thermal Gravimetric Analysis The temperatures of degradation of samples are determined by thermal gravimetric analysis (TGA). Approximately 20 mg of a sample is placed in a tared mold. The mold is then loaded in an oven. The air flows are left to balance. The sample is then heated to room temperature from 580 ° C to 10 ° C / min. The temperatures for weight loss of 1% and 5% of samples were reported respectively.

Ultraviolet-Visible Spectroscopy Ultraviolet-visible spectroscopy (UV-Vis) is used to monitor monomer consumption during the reaction. The reaction is allowed to continue until all monomers have been consumed. A Shimadzu UV-2450 UV-Vis spectrophotometer is used. Secondary measures were averaged over five measurements with an empty quartz tube. Aliquots were periodically taken from the reaction vessel, which was then placed in a square quartz tube having a beam distance of 1 cm. The absorbance of the sample is directly proportional in the concentration of the monomer in the aliquot. The progress of the reaction is monitored by UV-Vis spectroscopy with the characteristic absorption peak of β-farnesene at 230 nm.

Stress Resistance The voltage resistance of the samples is determined using an INSTRON ™ voltage tester. A sample is melted into films and cut to the appropriate dimensions. The thickness and width of the sample were measured after the procedure. A gauge length of 2.54 cm was used with a crosshead speed of 25 mm / min.

Union Test The binding test was used to characterize the adhesive properties of the samples. Two substrates are held together by an adhesive. The substrates are then disassembled, shearing the adhesive. The construction fails in one of three ways. When the substrate fails, it is called a substrate failure. When the adhesive tears, it is called a cohesive failure. When the interface between the substrate and the adhesive fails, it is called an adhesive failure. An INSTRON ™ tension tester was used to characterize the forces involved in the failure. The adhesive is applied to a 2 cm2 section of the substrate with a crosshead speed of 25 mm / min. Aluminum was used as the substrate. The aluminum it was cleaned with acetone before joining.

Nuclear Magnetic Resonance 1H and 13C Nuclear Magnetic Resonance XH and 13C is used to characterize chemical microstructures of samples. A Mercury Vary 300 MHz of NMR is used for these measurements. Deuterated chloroform was used as the solvent. Several measures were repeated to collect the spectrum.

Example 1 Non-ionic surfactant TERGITOL ™ 15-S-20 (obtained from Dow Chemical Co.), a nonionic surfactant secondary alcohol ethoxylate, was diluted from an activity of 79.50% to 15.33% with deionized water. AEROSOL ™ EF-810, an anionic sulfosuccinate surfactant (obtained from Cytec Industries Inc.), was used as it is in 30.10% activity.

In a 250 mL round bottom flask, 55.00 mL of deionized water was sprayed with nitrogen for at least 15 minutes to remove any dissolved oxygen.

The diluted TERGITOL ™ 15-S-20 (8.39 g) and AEROSOL ™ EF-810 (1.84 g) were added to the round bottom flask and stirred for at least 15 minutes. In a separate flask, 38.50g of farnesene, 70.40g of methyl methacrylate ("MMA"), and 1.10g of methacrylic acid ("MAA") and stirred to form a mixture. The mixture was added slowly to the water / surfactant mixture and stirred for about 15 minutes to form a pre-emulsion.

In a 500 mL four-necked round bottom flask equipped with a stirring shaft with a PTFE stirring blade; a capacitor; a temperature thermocouple with nitrogen inlet; and an inlet for the tubing of the syringe pump connected to the pre-emulsion, 90.00 mL of deionized water was sprayed with nitrogen gas for about 15 minutes.

The diluted TERGITOL ™ 15-S-20 (4.17 g) and AEROSOL ™ EF-810 (0.91 g) were added to the flask and stirred at 200 rpm for about 15 minutes under heat. The solution was heated to about 70 ° C. When the solution was around 65 ° C to about 70 ° C, sodium bicarbonate (0.55 g in 5.0 g deionized water) was added as a regulator.

The syringe pump was purged and the tube filled with the pre-emulsion. When the temperature was stabilized, 22 mL of the pre-emulsion (about 10%) was added to the flask at a rate of 7.5 mL / min.

After the addition of the pre-emulsion, the solution was stirred for about 2 minutes and then added the initiator of ammonium persulfate (0.55 g in 4.0g of deionized water) and stirred for about 15 minutes. The temperature of the solution increased by about 4-7 ° C.

After a reaction was initiated, 220 mL of the pre-emulsion was pumped into the flask for a period of three hours.

After the addition of the pre-emulsion was completed, the solution was maintained at about 70 ° C for about 30 minutes. The temperature of the flask was then raised and maintained at 75 ° C for 30 minutes. Then the flask temperature was raised and maintained at 80 ° C for 30 minutes. Finally, the temperature of the flask was raised and maintained at 85 ° C for 60 minutes and then a sample was analyzed by gas chromatography ("GC"). The GC analysis was used to measure the monomer conversion in the reaction.

The polymer in the flask was then cooled to room temperature and filtered in a suitable vessel. The weight average molecular weight and the polydispersity index ("PDI") of Example 1 were measured by size exclusion chromatography.

The polymer was dried in a vacuum oven at about 55 ° C for about two hours to remove the water. The glass transition temperature ("Tg") of Example 1 was measured by differential scanning calorimetry ("DSC") at a scanning speed of 10 ° C / min.

Example 2 The preparation procedure for Example 2 was the same as for Example 1, except that 44 g of farnesene (40% by weight) and 64.9 g of MMA (59.00% by weight) were used instead of 38.5 g of farnesene (35 g). % by weight) and 70.4 g of MMA (64% by weight). The weight average molecular weight, PDI and Tg of Example 2 are shown in Table 1.

Example 3 The preparation procedure for Example 3 was the same as for Example 1, except that 33 g of farnesene (30.00% by weight) and 75.9 g (69.00% by weight) of MMA were used instead of 38.5 g of farnesene (35 g). , 00% by weight) and 70.4 g of MMA (64.00% by weight). The weight average molecular weight, PDI and Tg of Example 3 is shown in Table 1.

Example 4 The preparation procedure for Example 4 was the same as for Example 1, except that 27.5 g of farnesene (25.00% by weight) and 81.4 g (74.00% by weight) of MMA were used instead of 38.5 g of farnesene (35%). % by weight) and 70.4 g of MMA (64% by weight). The weight average molecular weight, PDI and Tg of Example 4 are shown in Table 1.

Example 5 The preparation procedure for Example 5 was the same as for Example 1, except that 22 g of farnesene (20% by weight) and 86.9 g (79% by weight) of MMA were used instead of 38.5 g of farnesene (35%). % by weight) and 70.40 g of MMA (64% by weight). The weight average molecular weight, PDI and Tg of Example 5 are shown in Table 1.

Example 6 Example 6 was a comparative example. The preparation procedure for Example 6 was the same as for Example 1, except that 55 g of butyl acrylate ("BA") (50% by weight) and 53.9 g (49% by weight) of MMA were used instead of 38.5 g of farnesene (35.00% by weight) and 70.4 g of MMA (64% by weight). The weight average molecular weight, PDI and Tg of Example 6 is shown in Table 1.

Table 1 Example 7 The preparation procedure for Example 7 was the same as for Example 1, except that 35.2 g of farnesene (32% by weight) and 73.7 g (67% by weight) of MMA were used instead of 38.5 g of farnesene (35%). % by weight) and 70.4 g of MMA (64% by weight). The experiment was performed twice. The average weight average molecular weight values, PDI and Tg of Example 7 are shown in Table 2.

Example 8 The preparation procedure for Example 8 was the same as for Example 1, except that they were used 36. 3 g of farnesene (33% by weight) and 72.6 g (66% by weight) of MMA instead of 38.5 g of farnesene (35% by weight) and 70.4 g of MMA (64% by weight). The experiment was performed twice. The average weight average molecular weight values, PDI and Tg of Example 8 are shown in Table 2.

Example 9 The preparation procedure for Example 9 was the same as for Example 1, except that they were used 37. 4 g of farnesene (34% by weight) and 71.5 g (65% by weight) of MMA instead of 38.5 g of farnesene (35% by weight) and 70.4 g of MMA (64% by weight). The experiment was performed twice. The average values of the weight average molecular weight, PDI and Tg of Example 9 are shown in Table 2.

Example 10 The preparation procedure for Example 10 was the same as for Example 1, except that they were used 38. 5 g of farnesene (35% by weight) and 70.4 g (64% by weight) of MMA instead of 38.5 g of farnesene (35% by weight) and 70.4 g of MMA (64% by weight). The experiment was performed twice. The average values of the weight average molecular weight, PDI and Tg of Example 10 are shown in Table 2.

Example 11 The preparation procedure for Example 11 was the same as for Example 1, except that they were used 39. 6 g of farnesene (36% by weight) and 69.3 g (63% by weight) of MMA instead of 38.5 g of farnesene (35% by weight) and 70.4 g of MMA (64% by weight). The experiment was performed twice. The average values of the weight average molecular weight, PDI and Tg of Example 11 are shown in Table 2.

Example 12 Example 12 was a comparative experiment. The preparation procedure for Example 12 was the same as for Example 1, except that 55 g of BA (50% by weight) and 53.9 g (49% by weight) of MMA were used instead of 38.5 g of farnesene (35% by weight) and 70.4 g of MMA (64%). % in weigh). The experiment was performed twice. The average values of the weight average molecular weight, PDI and Tg of Example 12 are shown in Table 2.

Table 2 The conversion data of Table 2 shows that each of Examples 7-12 had a total monomer conversion greater than 99%. The Tg of Examples 1-5 and 7-11 are shown in Figure 1.

Example 13 The preparation procedure for Example 13 was the same as for Example 1, except that two additional ingredients were added to the pre-emulsion; and 44 g of farnesene (40% by weight), 11 g of BA (10% by weight) and 53.9 g of MMA (49% by weight) were used instead of 38.5 g of farnesene (35% by weight) and 70.4 g of MMA (64% by weight). The ingredients were 0.50 g of 1-dodecantiol and 1.00 g methyl-β-cyclodextrin. 1-dodecantiol was added as a chain transfer agent to prevent growth of the reaction polymer on itself. Methyl-β-cyclodextrin was added as a phase transfer agent to aid in the transport of both farnesene and 1-dodecantiol through the aqueous medium. The weight average molecular weight, PDI and Tg of Example 13 are shown in Table 3.

Example 14 The preparation procedure for Example 14 was the same as for Example 13, except that 33 g of farnesene (30% by weight) and 22 g of BA (20% by weight) were used instead of 44 g of farnesene (40% by weight). % by weight) and 11 g of BA (10% by weight). The weight average molecular weight, PDI and Tg of Example 14 are shown in Table 3.

Example 15 The preparation procedure for Example 15 was the same as for Example 13, except that 22 g of farnesene (20% by weight) and 33 g of BA (30% by weight) were used instead of 44 g of farnesene (40% by weight). % by weight) and 11 g of BA (10% by weight). The weight average molecular weight, PDI and Tg of the Example 15 is shown in Table 3.

Example 16 The preparation procedure for Example 16 was the same as for Example 13, except that 11 g of farnesene (10% by weight) and 44 g of BA (40% by weight) were used instead of 44 g of farnesene (40% by weight). % by weight) and 11 g of BA (10% by weight). The weight average molecular weight, PDI and Tg of Example 16 are shown in Table 3.

Example 17 Example 17 was a comparative example. The preparation procedure for Example 17 was the same as for Example 13, except that 55 g of BA (50% by weight) was used instead of 44 g of farnesene (40% by weight) and 11 g of BA (10%). % in weigh) . The weight average molecular weight, PDI and Tg of Example 17 is shown in Table 3.

Table 3 Examples 13-16 had a lower molecular weight and a lower PDI than in Example 17. The Tg of Examples 13-16 is shown in Figure 2.

Example 18 A mixture of 11.05 g of MMA (0.1104 moles), 67.69 g of β-farnesene (0.3312 moles) and 0.574 g of benzoyl peroxide ("BPO", 0.00237 moles) were added to a 250 ml three-necked round bottom flask. , equipped with a vertical agitator shaft with a PTFE stirring blade, in a glovebox with an N2 atmosphere. The ratio of farnesene to MMA was 3: 1. The flask was sealed and removed from the glove box, placed in a thermal blanket, and attached to a suspended agitator. An argon inlet was connected to the flask, as well as an oil bubbler. A stirring speed of 250 rpm was set on the suspended agitator and the flow of argon was adjusted in such a way that the argon bubbled through the bubbler at a rate of about 1 bubble per second. The heating mantle was set at 75 ° C and the reaction was allowed to continue for 15 hours. The heating mantle and the argon gas inlet were removed and 1.107 g of butylated hydroxytoluene ("BHT", 0.005024 mol) was added to the flask. The solution was stirred for 5 minutes before the polymer was precipitated from the solution. The precipitation was done by precipitating the solution again drip in 2 L of ice-cooled methanol. Once the polymer was precipitated, the methanol solution was decanted and the polymer was redissolved in tetrahydrofuran ("THF"). The resulting polymer solution in THF was precipitated in 2 L of ice-cooled methanol, and then the methanol solution was decanted. The polymer was redissolved in THF and re-precipitated in 2 L of ice-cooled methanol. The methanol was removed by decantation and the polymer was dried by removal of the residual solvent in a rotary evaporator and after placing the isolated polymer under vacuum (50 microns) overnight. A yield of 19.62 g (24.91%) of a clear, transparent, viscous liquid was obtained.

Example 18 was characterized by the following analytical data: XH NR (CDC13, 400 Hz): d = 5.2-5.0 (m, 30H), 4.8- 4.7 (s, 1H), 3.7-3.6 (s, 6H), 2.1-1.9 (m, 120H), 1.7-1.6 (s, 32H), 1.6 (s, 63H), 1.1 (m, 3H). 13 CNMR (THF-d8, 400 MHz): d = 135.9, 135.7, 131.8, 125.5, 125.4, 125.3, 40.9, 28.2, 28.1, 27.9, 26.6, 18.1, 16.5; GPC (THF, PS standards): Mw = 146 kDa, Mw / Mn = 2.4. DSC (2 ° C / min, N2): Tg (inflection) -66.15 ° C. The weight average molecular weight, PDI and Tg of Example 18 is shown in Table 4.

Example 19 The preparation procedure for Example 19 was the same as for Example 18, except that the ratio of farnesene to MMA was 1: 0. The following amounts of reagents were used: farnesene (79.008 g, 0.38661 moles), MMA (0 g, 0.0 moles), BPO (0.607 g, 0.00251 moles). The reaction was heated for 7 hours at 75 ° C before the addition of BHT (0.565 g, 0.00256 moles). A yield of 8.412 g (10.65%) of a clear, transparent, viscous liquid was obtained. The weight average molecular weight, PDI and Tg of Example 19 was measured and shown in Table 4.

Example 20 The preparation procedure for Example 20 was the same as for Example 18, except that the ratio of farnesene to MMA was 1: 0. The following amounts of reagents were used: farnesene (79.25 g, 0.3878 moles), MMA (0 g, 0.0 moles), BPO (0.607 g, 0.00251 moles). The reaction was heated for 18.5 hours at 75 ° C before the addition of BHT (1111 g, 0.005042 moles). A yield of 19,349 g (24.42%) of a clear, transparent, viscous liquid was obtained. The weight average molecular weight, PDI and Tg of Example 20 was measured and shown in Table 4.

Example 21 The preparation procedure for Example 21 was the same as for Example 18, except that the ratio of farnesin to MMA was 5: 1. The following amounts of reagents were used: farnesene (66,788 g, 0.32682 moles), MMA (6.54 g, 0.0653 moles), BPO (0.532 g, 0.00220 moles). The reaction was heated for 13.5 hours at 75 ° C before the addition of BHT (0.969 g, 0.00440 moles). A yield of 13,949 g (19.02%) of a clear, viscous liquid was obtained. The weight average molecular weight, PDI and Tg of Example 21 were measured and shown in Table 4.

Example 22 The preparation procedure for Example 22 was the same as for Example 18, except that the ratio of farnesene to MMA was 1: 1. The following amounts of reagents were used: farnesene (58.47 g, 0.2861 moles), MMA (26.17 g, 0.2614 moles), BPO (0.603 g, 0.00249 moles). The reaction was heated for 15.25 hours at 75 ° C before the addition of BHT (1102 g, 0.005001 moles). A yield of 29.98 g (35.42%) of a clear, transparent, viscous liquid was obtained. The weight average molecular weight, PDI and Tg of Example 22 were measured and shown in Table 4.

Example 23 The preparation procedure for Example 23 was the same as for Example 18, except that the ratio of farnesene to MA was 1: 1. The following amounts of reagents were used: farnesene (52.328 g, 0.25606 moles), MMA (25.633 g, 0.25602 moles), BPO (0.551 g, 0.00227 moles). The reaction was heated for 7.75 hours at 75 ° C before the addition of BHT (1,008 g, 0.004574 moles). A yield of 16,354 g (21.0%) of a clear, transparent, viscous liquid was obtained. The weight average molecular weight, PDI and Tg of Example 23 were measured and shown in Table 4.

Example 24 The preparation procedure for Example 24 was the same as for Example 18, except that the ratio of farnesene to MMA was 1: 2. The following amounts of reagents were used: farnesene (47.618 g, 0.23301 moles), MMA (46.659 g, 0.46603 moles), BPO (0.653 g, 0.00270 moles). The reaction was heated for 6 hours at 75 ° C before the addition of BHT (1196 g, 0.005427 moles). A yield of 19.7 g (20.9%) of a clear, transparent, viscous liquid was obtained. The weight average molecular weight, PDI and Tg of Example 24 were measured and shown in Table 4.

Example 25 The preparation procedure for Example 25 was the same as for Example 18, except that the ratio of farnesene to MMA was 1: 5. The following amounts of reagents were used: farnesene (29,842 g, 0.14603 moles), MMA (73,088 g, 0.73000 moles), BPO (0.690 g, 0.00285 moles). The reaction was heated for 6 hours at 75 ° C before the addition of BHT (1254 g, 0.005691 moles). A yield of 28,026 g (27.2%) of a white, opaque, hard solid was obtained. The weight average molecular weight, PDI and Tg of Example 25 were measured and shown in Table 4.

Example 26 The preparation procedure for Example 26 was the same as for Example 18, except that the ratio of farnesene to MMA was 1: 5. The following amounts of reagents were used: farnesene (29,839 g, 0.14601 moles), MMA (73,943 g, 0.73854 moles), BPO (0.691 g, 0.00285 moles). The reaction was heated for 4.25 hours at 75 ° C before the addition of BHT (1254 g, 0.00569 moles). A yield of 20,030 g (19.3%) of a white, opaque, hard solid was obtained. The weight average molecular weight, PDI and Tg of Example 26 were measured and shown in Table 4.

Table 4 Example 27 Example 19 (7,966 g) was dissolved in heptane (250 mL) and added to a Hastelloy 1 L pressure reactor, followed by 5% Pd / C catalyst (0.402 g). The reactor was sealed, placed in the reactor housing, and connected to a suspended agitator and a gas inlet. The solution was stirred at 240 rpm and the reactor was pressurized to 880 kPa with N2 gas. S.e observed the minimum pressure drop for 30 minutes. The reactor was evacuated and refilled with gas ¾ at 900 psi. The reactor was heated at 95 ° C for 2 hours and then the temperature was raised to 140 ° C. The reaction continued overnight before the pressure was released slowly. The solution was filtered through a plug of celite, concentrated under reduced pressure, and then dried under high vacuum (50 microns) overnight. The isolated polymer (7.608 g, 92.76%) was a transparent viscous liquid.

Example 27 was characterized by the following Analytical data: ½ NMR (THF-d8, 400 MHz): d = 1.6 to 1.5 (m, 6H), 1.5-1.0 (m, 100H), 0.9-0.8 (m, 50H). 13CNMR (THF-d8, 100 MHz): d = 39.4, 37.6, 37.4, 34.0. 32.8, 31.9, 28.0. 22.6, 22.3, 22.2, 19.3, 13.5; GPC (THF, PS Standards): Mw = 70 kDa, Mw / Mn = 1.6; DSC (2 ° C / min, N2): Tg (inflection) = -74.88 ° C. The weight average molecular weight, PDI and Tg of Example 27 are shown in Table 5.

Example 28 The preparation method was the same as in the Example 27, except that the polymer obtained from Example 20 (17,264 g) was dissolved in THF (800 mL) and the catalyst used was 5% Ru / C (0.902 g). The stirring speed was 300 rpm and the reactor was pressurized to 600 kPa with H2 gas. The reactor was heated to 140 ° C and the reaction was carried out overnight. A yield of 12,028g of a clear, viscous liquid was obtained. The weight average molecular weight, PDI, and Tg of Example 28 were measured and shown in Table 5.

Example 29 The method of preparation was the same as in Example 27, except that the polymer obtained from Example 21 (7883 g) was dissolved in heptane (820 mL) and the catalyst used was 5% Ru / C (0.394 g) . The stirring speed was 300 rpm and the reactor was pressurized to 600 kPa with H2 gas. The reactor was heated to 140 ° C and the reaction continued overnight. A yield of 7.666 g (99.88%) of a viscous, slightly turbid liquid was obtained. The weight average molecular weight, PDI, and Tg of Example 29 were measured and shown in Table 5.

Example 30 The method of preparation was the same as in Example 27, except that the polymer obtained from Example 18 (18.018 g) was dissolved in a 1: 1 volume-to-volume ratio of a mixture of ethyl acetate and heptane (850 mL) and the catalyst used was 5% Pd / C (0.906 g). The stirring speed was 300 rpm and the reactor was pressurized to 600 kPa with H2 gas. The reactor was heated to 140 ° C and the reaction continued overnight. A yield of 16,946 g (96.457%) of a slightly gray, translucent, viscous liquid was obtained. The weight average molecular weight, PDI, and Tg of Example 30 were measured and shown in Table 5.

Example 31 The preparation method was the same as in the Example 27, except that the polymer obtained from Example 22 (28.95 g) was dissolved in THF (800 mL) and the The catalyst used was 5% Pd / C (1453 g). The stirring speed was 300 rpm and the reactor was pressurized to 600 kPa with H2 gas. The reactor was heated to 140 ° C and the reaction continued overnight. A yield of 6,002 g of a translucent, slightly gray, highly viscous / vitreous material was obtained. The weight average molecular weight, PDI, and Tg of Example 31 were measured and shown in Table 5.

Example 32 The preparation method was the same as in Example 27, except that the polymer obtained from Example 23 (14.09 g) was dissolved in heptane (500 mL) and ethyl acetate (230 mL) and the catalyst used was Pd / C at 5% (0.706 g). The stirring speed was 250 rpm and the reactor was pressurized to 600 kPa with H2 gas. The reactor was heated to 140 ° C and the reaction continued overnight. A yield of 9,872 g (71.46%) of a slightly gray, translucent, highly viscous / vitreous solid was obtained. The weight average molecular weight, PDI, and Tg of Example 32 were measured and shown in Table 5.

Example 33 The preparation method was the same as in Example 27, except that the polymer obtained from the Example 24 (17.4 g) was dissolved in heptane (730 mL) and ethyl acetate (200 mL) and the catalyst used was 5% Pd / C (0.873 g). The stirring speed was 300 rpm and the reactor was pressurized to 600 kPa with H2 gas. The reactor was heated to 140 ° C and the reaction continued overnight. A yield of 13,666 g (79.7%) of a clear, glassy solid was obtained. The weight average molecular weight, PDI, and Tg of Example 33 were measured and shown in Table 5.

Example 34 The method of preparation was the same as in Example 27, except that the polymer obtained from Example 25 (22,674 g) was dissolved in THF (700 mL) and the catalyst used was 5% Ru / C (1138 g) . The stirring speed was 300 rpm and the reactor was pressurized to 600 kPa with H2 gas. The reactor was heated to 140 ° C and the reaction continued overnight. A yield of 16,477 g (73.296%) of a white, glassy solid was obtained. The weight average molecular weight, PDI, and Tg of Example 34 were measured and shown in Table 5.

Example 35 The method of preparation was the same as in Example 27, except that the polymer obtained from Example 26 (19.624 g) was dissolved in THF (800 mL) and the The catalyst used was 5% Ru / C (0.993 g). The stirring speed was 300 rpm and the reactor was pressurized to 600 kPa with H2 gas. The reactor was heated to 140 ° C and the reaction continued overnight. A yield of 11.863 g (60.973%) of a gray or white glassy solid was obtained. The weight average molecular weight, PDI, and Tg of Example 35 were measured and shown in Table 5.

Table 5 Example 36 Maleic anhydride (34.323 g, 0.3500 mol), benzoyl peroxide (2.921 g, 0.01206 mol) and dioxane (190 mL) were added in a three-necked round bottom flask, equipped with a suspended stirrer, an argon inlet and a addition funnel. The suspended agitator was adjusted to a stirring speed of 250 rpm and the solution was purged with argon for about 35 minutes. The flask is placed in a heating block and the solution was heated to around 30 ° C. Meanwhile, diethylaniline (0.627 g, 0.00425 mole), β-farnesene (71.510 g, 0.34992 mole) and dioxane (50 mL) were added to the funnel and the diethylaniline solution was sprayed with argon for about 15 minutes. The diethylaniline solution was added dropwise in the flask for 4.5 hours. The heating block was removed from the flask, butylated hydroxytoluene (2.644 g, 0.01200 mol) was added to the flask, and stirred for 5 minutes. The solution was precipitated in 2 L of ice-cooled methanol while the methanol was agitated with a stirrer suspended at 500 rpm. The polymer precipitated as a large, pink mass of fibers and the methanol solution turned pink. The methanol solution was decanted and the polymer was redissolved in dioxane (250 mL) and re-precipitated in 2 L of ice-cooled methanol. The methanol solution was decanted and the polymer was redissolved in dioxane (250 mL) and re-precipitated in 2 1 of ice-cooled methanol. The methanol was decanted again and the polymer was redissolved in dioxane (250 mL) and re-precipitated in 2 L of ice-cooled methanol. The methanol from the third precipitation was decanted and the polymer was dried under high vacuum (50 microns) overnight to give 29.65 g (28.02%) of a yellow-brown hard solid. Example 36 was characterized by the following data analytical: ½ NMR (dioxane-d8, 400 MHz): d = 5.0-4.8 (m, 3H), 3.6-3.3 (m, 9H), 2.6-2.3 (m, 2H), 2.3 -2.0 (s, 3H) , 1.9-1.7 (m, 7H), 1.5-1.3 (m, 9H); 13 C NMR (dioxane-d 8, 400 MHz): d = 174, 173, 135.0, 130.6, 124.2, 124.2, 123.8, 50.7, 39.5, 26.4, 25.2, 24.9, 16.9, 15.3; GPC (THF, PS Standards): Mw = 55 kDa, Mw / Mn = 1.4; DSC (2 ° C / min, N2): Tg (inflection) = 8.85 ° C.

Example 37 Styrene (11.50 g, 0.1104 moles), ß-farnesin (67.69 g, 0.3312 moles) and benzoyl peroxide (0.574 g, 0.00237 moles) were added to a 250 mL three-necked round bottom flask, equipped with a vertical shaker shaft with a PTFE stirring blade, in a box of gloves with an atmosphere of N2. The flask was hermetically sealed and removed from the glove box, placed in a thermal blanket and attached to a suspended agitator. An argon inlet was connected to the flask, as well as an oil bubbler. A stirring speed of 250 rpm is found in the suspended agitator and the flow of argon was adjusted in such a way that the argon bubbled through the bubbler at a rate of about 1 bubble per second. The heating mantle was set at about 75 ° C and the reaction was allowed to continue for 15 hours. The heating mantle and the argon gas inlet were removed and added butylated hydroxytoluene (1,107 g, 0.005024 mol) in the flask. The resulting solution was allowed to stir for five minutes before the polymer was precipitated from the solution. Precipitation was carried out by dripping, the resulting solution dripping in 2 L of methanol was cooled with ice. Once the polymer is precipitated, the methanol solution is decanted and the polymer is redissolved in tetrahydrofuran (THF). The resulting polymer solution in THF was precipitated in ice-cooled methanol (2 L), and the methanol solution was decanted. The polymer was redissolved in THF again and re-precipitated in ice-cold methanol (2 L), the methanol was decanted, and the polymer was dried. The polymer is dried by removing the residual solvent in a rotary evaporator and after placing the isolated polymer under vacuum (50 microns) overnight.

Example 38 The preparation procedure for Example 38 was the same as for Example 1, except that 35.2 g of farnesene (32% by weight) and 73.7 g (67% by weight) of MMA were used instead of 38.5 g of farnesene (35%). % by weight) and 70.4 g of MMA (64% by weight). The weight average molecular weight of Example 38 was 193 kDa. The Tg of Example 38 was 15.32 ° C.

Example 39 The preparation procedure for Example 39 was the same as for Example 1, except that 37.4 g of farnesene (34% by weight) and 71.5 g (65% by weight) of MMA were used instead of 38.5 g of farnesene (35%). % by weight) and 70.4 g of MMA (64% by weight). The weight average molecular weight of Example 39 was 169 kDa. The Tg of Example 39 was 12.86 ° C.

Example 40 The preparation procedure for Example 40 was the same as for Example 1, except that 39.6 g of farnesene (36% by weight) and 69.3 g (63% by weight) of MMA were used instead of 38.5 g of farnesene (35%). % by weight) and 70.4 g of MMA (64% by weight). The weight average molecular weight of Example 40 was 157 kDa. The Tg of Example 39 was 5.24 ° C.

Example 41 Example 41 was a film prepared from the emulsion obtained from Example 6 the emulsion was applied on an aluminum panel using a square reduction giving a wet film with a thickness of about 0.127 mm (ie, 5 mils of inch).

No coalescing agent was added to the emulsion. The films were dried in a forced air oven at 45 ° C for 10 minutes and then conditioned for 7 days at a temperature of 22.22 ° C +/- 15.00 ° C (72 ° F +/- 5 ° F) and 50 % relative humidity +/- 10%.

Example 42 Example 42 was prepared according to the procedure for Example 41, except that the emulsion was obtained from Example 38.

Example 43 Example 43 was prepared according to the procedure for Example 41, except that the emulsion was obtained from Example 39.

Example 44 Example 44 was prepared according to the procedure for Example 41, except that the emulsion was obtained from Example 40.

Minimum Film Formation Temperature ("MFFT") The MFFT Test could be carried out in accordance with the American Society for Testing Materials ("ASTM") test D2354-10, entitled "Standard Test Method for the Emulsion Vehicle Film Minimum Formation Temperature ", which is incorporated herein by reference, A method for determining the minimum temperature at which the emulsion vehicles are attached to form a continuous film is provided.

The films obtained from Examples 41-44 were tested with the MFFT test. The MFFT test was carried out with a Rhopoint 90 instrument in accordance with ASTM D2354-10. The minimum film-forming temperature of Examples 41-44 was measured and shown in Table 6 below.

Table 6 Pencil Hardness The pencil hardness test evaluates the hardness of film coatings when they are scratched by lead pencils. This test could be carried out in accordance with the ASTM D3363-05 test, entitled "Method Test Standard for Hardness Film by Pencil Test ", which is incorporated herein by reference Standard pencils of varying lead softness of 6B to 8H are used.The hardness scale (softest to hardest) is 6B < 5B < 4B < 3B < 2B < B < HB < F < H < 2H < 3H < 4H < 5H < 6H < 8H. A rating of 6B indicates that the The film is very soft, a rating of 8H indicates a film is extremely hard.

The test involved the following stages. First, the films can be formed from an emulsion obtained from any of Examples 1-40. A pencil is placed on the surface of the film. The pencil is held at about 45 ° and is pushed around 5 cm / sec. The film is scratched by using harder pencils in succession until the film is damaged. At this point, the lead that first spoils the film is considered to be the hardness of the pencil in the film.

The hardness of the pencil in the films obtained from Examples 41-44 was measured in accordance with ASTM D3363-05. The results are shown in Table 7 below.

Table 7 Block resistance test The dried films obtained from Examples 6 and 38-40 were tested with the Block Resistance Test. The Block Resistance Test was performed in accordance with ASTM 2793-99. The test was performed in the "face-to-face" condition using a Sag paper and the Leveta Co. 7B Leveling Test chart (Mahwah, NJ) as the substrate. The emulsions of Examples 6 and 38-40 were applied to the substrate using a square reduction giving a wet film having a thickness of about 0.127 mm [ie, 5 mils]. The films were dried in a forced air oven at 45 ° C for ten minutes and then kept at room temperature for seven days. The substrate was folded back on itself so that the film came in contact with itself and a weight of 1 kilogram was placed on the top of the substrate for 1 hour, 24 hours and 48 hours. The results of the test are shown in Table 8. A rating of "10" means that there is no adherence between the films, while a rating of "1" means that there is a 100% seal between the films.

Table 8 Examples 38-40 had a block resistance rating of 7 or greater after 48 hours, while Example 6 failed after 24 hours.

Accelerated Film Aging Test This test could be carried out in accordance with the ASTM D4587 test, which is incorporated herein by reference. The capacity of the film to resist the deterioration of its physical and optical properties caused by exposure to light, heat and humidity was determined. This provided a method for the selection of test conditions for accelerated exposure testing of products in fluorescent ultraviolet ("UV") light and condensing devices. The test was carried out with repeated cycles of exposure to fluorescent UV light and the condensation. The films can be formed from examples 1-40. Movies can be tested with a duration of 250 and 500 hours.

This test may also be performed in accordance with ASTM Test G154, entitled "Standard Practice for Apparatus That Operates with Fluorescent Light for UV Exposure of Non-Metallic Materials", which are incorporated herein by reference. The method uses fluorescent UV light, and water appliances to reproduce the weathering effects that occur when materials are exposed to sunlight (either directly or through the glass window) and moisture in the form of rain or dew in actual use. The test samples are exposed to fluorescent UV light under controlled environmental conditions. This test method calculates a value for ??, a numel value which represents any change in clarity of the film and any change in the color of the film. Any value less than 1 can not be detected with the naked eye and is considered to happen. A 340 A bulb was used in the test and the measurements were taken at 144, 250 and 500 hours.

Resistance to change in color and luminosity under UV light exposure for films obtained from Examples 41-44 were tested in accordance with ASTM G154. The results of the tests are shown in the Table 9 Table 9 Standard Test Method for the Effect of Household Chemicals on Transparent and Pigmented Organic Films This test could be carried out in accordance with the ASTM D1308 test, | which is incorporated herein by reference. The test provides a method for determining the effect of chemicals on transparent and pigmented organic films resulting in any objectionable surface alteration, such as discoloration, gloss change, blistering, softening, swelling, loss of adhesion, or phenomena. special The chemicals used may include one or more ethyl alcohol, isopropyl alcohol ("IPA"), xylene, acid or alkaline solutions, soap or detergent solutions, oil or fat and the like. The films were formed from Examples 1-6. The sample can be Double friction (ascending and descending movement) with IPA.

This test may also be performed in accordance with ASTM Test D4752-10, entitled "Standard Practice for Measurement of MEK Resistance of Ethyl Silicate (Inorganic) Zinc-Rich Primers with Friction Solvent", which is incorporated herein for reference. The films obtained from Examples 41-44 were tested in accordance with ASTM D4752. A weight of two pounds was wrapped in gauze, soaked in isopropanol, and then dragged back and forth on a film panel until cracks began to appear on the film. A run was considered by dragging the weight back and forth on the panel. The results are shown in Table 10. The greater the number of runs, the better the integrity of the film and the resistance to isopropanol.

Table 10 Example 41 did not pass the test. Examples 42-44 approved the test. Samples 42-44 were considered for having good chemical resistance and integrity of the film when exposed to double friction with isopropanol.

Chemical Stain Test Another test for chemical resistance is known as the Chemical Stain Test, where a drop of a common household chemical was applied, such as isopropanol, ethyl alcohol, vinegar and Fantastik cleaning formulation from the SC Johnson Company or "stained" in a dry film of Examples 41-44.

The films were evaluated for the softening and color change tests after 15 minutes and 1 hour of exposure. The results are shown in Tables 11-12. The films were rated from 1 to 5. A rating of "5" meant that the best movie does not show softening or color change and a rating of "1" meant the worst.

Table 11 It was not possible to evaluate due to the lack of integrity film after the application of solvents.

Table 12 NA - It was not possible to evaluate due to the lack of integrity of the film after the application of solvents.

Examples 41-44 were tested by the above tests. The films obtained from Examples 1 to 37 could also be tested by the above tests.

While the invention has been described with respect to a limited number of embodiments, the specific characteristics of a modality should not be attributed to other embodiments of the invention. Not only the modality is representative of all aspects of the invention. In some embodiments, compositions or methods may include numerous compounds or steps not mentioned herein. In other embodiments, the compositions or methods do not include, or are substantially free of any compound or steps not mentioned herein. There are variations and modifications of the modalities described. Finally, any number described here must be interpreted in the sense of approximation, regardless of whether the word "about" or "approximately" is used to describe the number. The appended claims are intended to cover all those modifications and variations that fall within the scope of the invention.

Claims

1. An emulsion polymerization composition, characterized in that it comprises: a) a polymerizable mixture comprising a farnesene and at least one vinyl monomer; b) at least one emulsifier; c) at least one free radical initiator; and d) water.

2. The composition according to claim 1, characterized in that the farnesene is o-farnesene or β-farnesene or a combination thereof.

3. The composition according to any of claims 1-2, characterized in that the farnesene is in an amount greater than 20% by weight, based on the total weight of the polymerizable mixture.

4. The composition according to any of claims 1-2, characterized in that the farnesene is in an amount greater than 50% by weight, based on the total weight of the polymerizable mixture.

5. The composition according to any of claims 1-4, characterized in that at least one vinyl monomer is styrene, substituted styrene, a diene of 4-40 carbon atoms, a vinyl halide, vinyl ether, vinyl acetate, vinyl pyridine, vinylidene fluoride, acrylonitrile, acrylic acid, an acrylic ester, acid methacrylic, a methacrylic ester, acrylamide, methacrylamide or a combination thereof.

6. The composition according to any of claims 1-4, characterized in that at least one vinyl monomer comprises methacrylic acid and a methacrylic ester, which is optionally methyl methacrylate.

7. The composition according to claim 6, characterized in that the methacrylic acid is in an amount of from about 0.1% by weight to about 5% by weight, or from about 10% by weight to about 40% by weight, based on the total weight of the polymerizable mixture.

8. The composition according to claim 6, characterized in that at least one vinyl monomer further comprises an acrylic ester, which is optionally butyl acrylate.

9. The composition according to any of claims 1-4, characterized in that at least one vinyl monomer comprises methacrylic acid and styrene.

10. The composition according to any of claims 1-4, characterized in that the free radical initiator is a water-soluble free radical initiator, which is optionally ammonium peroxomonosulfate, ammonium peroxodisulfate, potassium peroxomonosulfate, potassium peroxodisulfate, peroxomonosulfate sodium, sodium peroxodisulfate, hydrogen peroxide, a redox initiator or a combination thereof.

11. A method for the emulsion polymerization of a farnesene with at least one vinyl monomer, characterized in that the method comprises copolymerizing the farnesene with at least one vinyl monomer in an aqueous medium in the presence of at least one free radical initiator and at least one an emulsifier.

12. The method according to claim 11, characterized in that the farnesene is α-farnesene or β-farnesene or a combination thereof.

13. The method according to any of claims 11-12, characterized in that the farnesene is in an amount greater than 20% by weight, based on the total weight of the polymerizable mixture.

14. The method according to any of claims 11-12, characterized in that the farnesene is in an amount greater than 50% by weight, based on the total weight of the polymerizable mixture.

15. The method according to any of claims 11-14, characterized in that at least one vinyl monomer is styrene, substituted styrene, a diene of 4-40 carbon atoms, a vinyl halide, vinyl ether, vinyl acetate, vinyl pyridine, vinylidene fluoride, acrylonitrile, acrylic acid, an acrylic ester, acid methacrylic, a methacrylic ester, acrylamide, methacrylamide or a combination thereof.

16. The method according to any of claims 11-15, characterized in that at least one vinyl monomer comprises methacrylic acid and a methacrylic ester, which is optionally methyl methacrylate.

17. The method according to claim 16, characterized in that the methacrylic acid is in an amount of from about 0.1% by weight to about 5% by weight, or from about 10% by weight to about 40% by weight, based on the total weight of the polymerizable mixture.

18. The method according to claim 16, characterized in that at least one vinyl monomer further comprises an acrylic ester, which is optionally butyl acrylate.

19. The method according to any of claims 11-14, characterized in that at least one vinyl monomer comprises methacrylic acid and styrene.

20. The method according to any of claims 11-19, characterized in that the free radical initiator is a water-soluble free radical initiator, which is optionally ammonium peroxomonosulfate, ammonium peroxodisulfate, potassium peroxomonosulfate, potassium peroxodisulfate, sodium peroxomonosulfate, sodium peroxodisulfate, hydrogen peroxide, a redox initiator or a combination thereof.

21. A method for preparing a polymer emulsion, characterized in that it comprises: (a) providing an aqueous emulsion comprising a polymerizable mixture comprising a farnesene and at least one vinyl monomer; at least one emulsifier; at least one initiator; And the water; Y (b) emulsion polymerization in at least a portion of the polymerizable mixture to form the polymer emulsion.

22. The method in accordance with the claim 21, characterized in that it further comprises drying the polymer emulsion to form an emulsion polymer.

23. The method in accordance with the claim 22, characterized in that the emulsion polymer is in powder or film form.

24. The method according to any of claims 21-23, characterized in that the farnesene is o-farnesene or β-farnesene or a combination thereof.

25. The method according to any of claims 21-24, characterized in that the farnesene is in an amount greater than 20% by weight, based on the total weight of the polymerizable mixture.

26. The method according to any of claims 21-24, characterized in that at least one Vinyl monomer is styrene, substituted styrene, a diene of 4-40 carbon atoms, a vinyl halide, vinyl ether, vinyl acetate, vinyl pyridine, vinylidene fluoride, acrylonitrile, acrylic acid, an acrylic ester, methacrylic acid, an ester methacrylic, acrylamide, methacrylamide or a combination thereof.

27. The method according to any of claims 21-24, characterized in that at least one vinyl monomer comprises methacrylic acid and a methacrylic ester, which is optionally methyl methacrylate.

28. The method according to claim 27, characterized in that the methacrylic acid is in an amount of from about 0.1% by weight to about 5% by weight, or from about 10% by weight to about 40% by weight, based on the total weight of the polymerizable mixture.

29. The method according to claim 27, characterized in that at least one vinyl monomer further comprises an acrylic ester, which is optionally butyl acrylate.

30. The method according to any of claims 21-24, characterized in that at least one vinyl monomer comprises methacrylic acid and styrene.

31. The method according to any of claims 21-30, characterized in that the free radical initiator is a soluble free radical initiator in water, which is optionally ammonium peroxomonosulfate, ammonium peroxodisulfate, potassium peroxomonosulfate, potassium peroxodisulfate, sodium peroxomonosulfate, sodium peroxodisulfate, hydrogen peroxide, or a redox initiator or a combination thereof.

32. A polymer emulsion characterized in that it is prepared by the method according to any of claims 21 and 24-31.

33. An emulsion polymer prepared by the method according to claim 22, characterized in that the emulsion polymer comprises a farnesin interpolymer, and wherein the farnesene is in an amount of at least about 25 mole percent, based on the total moles of the farnesin interpolymer.

34. A method for copolymerizing a polymerizable mixture in the presence of at least one free radical initiator to form a farnesene interpolymer, characterized in that the polymerizable mixture comprises a farnesene and at least one vinyl monomer, wherein at least one free radical initiator is hydrogen peroxide, a hydroperoxide, a dialkylperoxide, a diacylperoxide, a peroxyester, a peroxyketone, an azo compound, an organic polyoxide, a photoinitiator, a persulfate or a combination thereof.

35. The method in accordance with the claim 34, characterized in that the farnesene is in an amount greater than 20% by weight, based on the total weight of the polymerizable mixture.

36. The method according to any of claims 34-35, characterized in that the farnesene is α-farnesene or β-farnesene or a combination thereof.

37. The method according to any of claims 34-36, characterized in that at least one vinyl monomer is styrene, substituted styrene, a diene of 4-40 carbon atoms, a vinyl halide, vinyl ether, vinyl acetate, vinyl pyridine, vinylidene fluoride, acrylonitrile, acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester, acrylamide, methacrylamide or a combination thereof.

38. The method according to any of claims 34-36, characterized in that at least one vinyl monomer comprises a methacrylic ester, styrene, butadiene, isoprene, myrcene, or a combination thereof. SUMMARY OF THE INVENTION Polyphanesphenes are provided herein, such as farnesene homopolymers derived from a farnesene and farnesene interpolymers derived from a farnesene and at least one vinyl monomer; and processes to make and use polypharmames. The homopolymer of farnesene can be prepared by polymerizing farnesene in the presence of a catalyst. In some embodiments, farnesene is prepared from a sugar by using a microorganism.